1. Stoichiometric Reactivity of Proton Transfer Cooperative
Complexes
Elias El-Zouki
Blacquiere Group
Department of Chemistry
Western University
A thesis submitted in partial fulfillment of the requirements for the degree
Honors Bachelor of Science (Chemistry)
March 2016

2. ii
Approved for the Department of Chemistry:
Dr. Brian L. Pagenkopf
Dr. James A. Wisner
Dr. Johanna M. Blacquiere

3. iii
Acknowledgments
First and foremost I would sincerely like to thank Prof. Johanna Blacquiere for her
continuous support throughout the duration of this project. Johanna was consistently
available to answer any questions I had and often made an effort to see how things were
going. I learned a lot under the guidance of Johanna. In particular, I discovered an interest
for research I previously did not know existed. I do not know if this same interest would
exist today had I not conducted this project under Johanna’s supervision.
I would like to thank James Stubbs for teaching me many of the laboratory techniques
used to complete this project and his consistent words of advice. Ethan Sauve is thanked
for always being up for a game of chess. I would also like to thank the other members of
the Blacquiere group for their encouragement and constructive criticism: Ava Behnia,
Scott William Hendriks, Sydney Elizabeth Davenport (Lizzy), and Jennifer Yuan.
The Puddephatt, Ragogna, and Stillman group are thanked for lending chemicals and
glassware. The Chemistry Facility at Western University are also thanked for their
assistance: Mat Willans (NMR spectrometry), Paul Boyle (X-ray diffraction facility),
Yves Rambour (glassblowing), and Kristina Jurcic (MALDI data). Additionally I thank
my friends and family for their support and encouragement.

4. iv
Table of Contents
Abstract......................................................................................................................................... vi
List of Abbreviations .................................................................................................................. vii
List of Figures.............................................................................................................................viii
List of Tables ................................................................................................................................ ix
List of Schemes............................................................................................................................. ix
1.0 Introduction............................................................................................................................. 1
1.1 Metal-Ligand Cooperative Complexes................................................................................................1
1.2 Proton-Transfer Metal-Ligand Cooperative Complexes.....................................................................1
1.3 Tunable PR
2NR′
2 Ligands .....................................................................................................................2
1.4 Hydration of Terminal Alkynes Using Proton Transfer MLC Catalysts ............................................3
1.5 [Ru(Cp)(PR
2NR’
2)(NCMe)][PF6] In Hydration of Terminal Alkynes ..................................................4
1.6 [Ru(Cp)(PR
2NR’
2)(NCMe)][PF6] In Acceptorless Dehydrogenation Reactions ..................................5
1.7 Scope of Thesis....................................................................................................................................5
2.0 Results and Discussion............................................................................................................ 6
2.1 Improved Synthesis of [Ru(Cp)(PtBu
2NBn
2)(NCMe)][PF6] ..................................................................6
2.2 Preliminary Stoichiometric Studies of 1 with an Internal Alkyne ......................................................7
2.3 Stoichiometric Reactivity Studies of 1 and 2 with H2 .........................................................................8
2.4 Preparation of the Ru-H Complex 3 from 1 ........................................................................................9
2.5 Preliminary Stoichiometric Preparation of Ru(Cp)(PPh
2NBn
2)(NCMe)(H) Complex 4 from
Complex 2 ...............................................................................................................................................13
2.6 Preparation of the Ru-H Complex 3 from the Ru-Cl Complex 5......................................................14
2.7 Stoichiometric Reactivity Studies of Ru-H Complex (3) with Acid Under Closed
Conditions................................................................................................................................................15
2.8 Stoichiometric Reactivity Studies of Ru(Cp)(PtBu
2NBn
2)(NCMe)(H) with Acid Under
Conditions Allowing for H2 Release From NMR Tube ..........................................................................17
3.0 Conclusion ............................................................................................................................. 18
3.1 Compound Synthesis .......................................................................................................... 18
3.2 Stoichiometric Reactivity Studies....................................................................................... 19
4.0 Future Investigations............................................................................................................ 19
5.0 Experimental ......................................................................................................................... 20
5.1 General Procedures............................................................................................................................20

5. v
5.2 Preliminary Studies of 1 and Ethyl Phenylpropiolate .......................................................................20
5.3 Stoichiometric Reactivity Studies of 1 and 2 with H2 .......................................................................21
5.4 Preliminary Stoichiometric Preparation of 4 from 2 .........................................................................21
5.5 Reactivity Studies of 3 and [HDMF][OTF] Under Closed Conditions.............................................21
5.6 Reactivity Studies of Ru-H Complex (3) and [HDMF][OTF] Under Open Conditions...................22
5.7 Synthesis of Ru(Cp)(PtBu
2NBn
2)(NCMe)][PF6] ..................................................................................22
5.8 Synthesis of Ru(Cp)(PPh
2NBn
2)(NCMe)][PF6] ...................................................................................22
5.9 Synthesis of 3 from 5.........................................................................................................................23
5.10 Synthesis of 3 from 1.......................................................................................................................23
6.0 References.............................................................................................................................. 24
7.0 Appendix................................................................................................................................. A
7.1 NMR Spectra......................................................................................................................................A
7.2 X-Ray Diffraction Crystallography Data .......................................................................................... H

6. vi
Abstract
Ru(Cp)(PtBu
2NBn
2)(MeCN)][PF6] and Ru(Cp)(PPh
2NBn
2)(MeCN)][PF6] are
cooperative complexes previously prepared by the Blacquiere group that are capable of
performing the acceptorless dehydrogenation of benzylamine. The extreme catalytic
conditions suggest there is a slow step within the proposed catalytic cycle hindering
turnover. An array of stoichiometric reactivity studies with these complexes were
performed to better understand the proposed catalytic cycle. The complexes were treated
with a set of reagents that include: dihydrogen gas, acids, and hydride donors.

7. vii
List of Abbreviations
AD Acceptorless dehydrogenation
ADC Acceptorless dehydrogenation coupling
Bn Benzyl
Cp Cyclopentadiene
Cp* Pentamethylcyclopentadiene
DCM Dichloromethane
DMF Dimethylformamide
Equiv Equivalence
h Hour
HDMF Dimethylformamide, protonated
MALDI Matrix Assisted Laser Desorption Ionization
MLC Metal ligand cooperative
NMR Nuclear Magnetic Resonance
OPPh3 Triphenylphosphine Oxide
OTF Trifluoromethanesulfonate
Ph Phenyl
ppm Parts per million
PR
2NR’
2 1,5-diaza-3,7-diphosphacyclooctane ring
RT Room temperature
t
Bu tert-butyl
THF Tetrahydrofuran
TM Transition metal

8. viii
List of Figures
Figure 1. MLC complexes capable of proton transfer. Basic and acidic sites are respectively
shown in blue and red. ..................................................................................................................... 2
Figure 2. a) The structure of the PR
2NR′
2 family of ligand and b) typical coordination of the
ligand to a metal center (M)............................................................Error! Bookmark not defined.
Figure 3. PT MLC catalysts capable of performing anti-Markovnikov hydration of terminal
alkynes. ............................................................................................................................................ 4
Figure 4. Derivatives of Ru(Cp)(PR
2NR’
2)(NCMe)][PF6]. ............................................................. 5
Figure 5. 31
P{1
H} NMR (243 MHz, Acetone) spectra of an unknown species formed when 1 is
allowed to react with ethyl phenylpropiolate................................................................................... 8
Figure 6. 31
P{1
H} NMR spectra (243 MHz, DMF) monitoring the reaction of 1 with H2 at 110
°C: a) 1 (54.9 ppm) at 0 h of H2 exposure, b) 1-H2 (60.3 ppm) at 4 h of H2 exposure, c) 1-H2 (60.3
ppm) at 24 h of H2 exposure. ........................................................................................................... 9
Figure 7. MALDI-MS analysis of 3 with an anthracene matrix. m/z values are reported in insets
with the simulated spectrum at the top and the experimental spectrum at the bottom. ................. 11
Figure 8. X-ray crystal structure of 3. Thermal ellipsoids are shown at a 50% probability. H1
H
indicates the hydride ligand. Hydrogen atoms and t
Bu groups on the PtBu
2NBn
2 ligand were
removed for clarity......................................................................................................................... 12
Figure 9. 31
P{1
H} NMR spectra (242 MHz) of 3 after 48 hours in the solvents: a) MeCN-d3,
where 1 has formed, b) CDCl3 where 5 has formed, and c) C6D6. ................................................ 13
Figure 10. 31
P{1
H} NMR spectra (243 MHz) monitoring the stoichiometric formation of 4 (48.1
ppm) from 2 (39.9 ppm): a) 0 h (THF), b) 1.5 h (THF), c) 11 h (THF), d) 22 h (C6D6). .............. 14
Figure 11. 31
P{1
H} NMR spectra (243 MHz, CD2Cl2) of a) 3; and mixtures of 3 with b) 0.2
equiv [HDMF][OTF]; c) 0.4 equiv [HDMF][OTF]; d) 0.6 equiv [HDMF][OTF]; e) 0.8 equiv
[HDMF][OTF], f) 1.0 equiv [HDMF][OTF]; and g) 1.0 equiv [HDMF][OTF] analyzed after 24 h.
Compound 5 is observed as a competitive decomposition product............................................... 16
Figure 12. 1
H NMR spectra (599 MHz, CD2Cl2) of a) 3; and mixtures of 3 with b) 0.2
equiv [HDMF][OTF]; c) 0.4 equiv [HDMF][OTF]; d) 0.6 equiv [HDMF][OTF]; e) 0.8
[HDMF][OTF]; f) 1.0 equiv [HDMF][OTF]. The spectra had a region of peak
suppression at 1.90 – 2.00 ppm to remove the large singlet belonging to the methyl
hydrogens of MeCN.......................................................................................................... 17

9. ix
Figure 13. 31
P{1
H} NMR spectra (243 MHz, CD2Cl2) of a) 3; and mixtures of 3 with b)
0.5 equiv [HDMF][OTF]; c) 1.0 equiv [HDMF][OTF]; and 1.0 equiv [HDMF][OTF]
analyzed after 24 h............................................................................................................ 18
List of Tables
Table 1. Selected bond lengths (Å) and angles (˚) for complexes 1,7
and 3. .............................. 12
List of Schemes
Scheme 1. A) A traditional catalytic cycling using a TM catalyst B) The catalytic cycle of an
MLC complex: M = metal-center, L = non-cooperative ligand, Lx
= cooperating ligand, S =
substrate, I = intermediate, P = product. ......................................................................................... 1
Scheme 2. Proposed mechanism for the anti-Markovnikov hydration of terminal alkynes using a
proton transfer MLC catalyst: B = Basic site of ligand. ................................................................. 4
Scheme 3. Synthesis of a deactivated through a postulated vinylidene intermediate.6
................. 5
Scheme 4. The catalytic conversion of benzylamine to give the AD and ADC products. ........... 5
Scheme 5. Proposed mechanism for the AD of benzylamine using 1 and 2. ............................... 6
Scheme 6. Improved synthetic route to 1 using a 1:1 mixture of MeCN and DCM for the
phosphine ligation. .......................................................................................................................... 7
Scheme 7. Reaction of 1 with an internal alkyne to give possible products: A π-bound alkyne
(A), vinylidene (B) or a vinyl ammonium (C). ............................................................................... 8
Scheme 8. Treatment of 1 and 2 with dihydrogen gas. ................................................................. 9
Scheme 9. Synthesis of 3 via hydride transfer. ........................................................................... 10
Scheme 10.Stoichiometric synthesis of 4 via hydride transfer.................................................... 13
Scheme 11. Synthesis of 3 via ligand substitution from 5. ......................................................... 15
Scheme 12. Probing the reactivity of 3 with acid in dichloromethane and acetonitrile. ............ 15
Scheme 13. A proposed mechanistic study of forming 1-H2. ..................................................... 20

10. 1
1.0 Introduction
1.1 Metal-Ligand Cooperative Complexes
A catalyst is a substance that will decrease a reaction’s activation energy but is not consumed
during the process.1,2
Synthetic homogeneous transition metal (TM) catalysts contain a central
metal atom coordinating to surrounding organic fragments (ligands). The electronic and steric
properties of the ligands, and the nature of the metal center will dictate the properties of the
organometallic catalyst.3
Atoms covalently bonded to the metal make up the primary coordination sphere, where
reactivity with a substrate traditionally occurs (Scheme 1A). A metal-ligand cooperative (MLC)
complex utilizes both the primary and second coordination spheres to mechanistically assist in
the formation of product (Scheme 1B).4
This ability can sometimes lead to MLC complexes
having advantages over traditional non-cooperative complexes, such as allowing catalysis to be
conducted under milder conditions and/or the catalyst may have increased turnover frequency.5
Scheme 1. A) A traditional catalytic cycling using a TM catalyst B) The catalytic cycle of an MLC complex: M =
metal-center, L = non-cooperative ligand, Lx
= cooperating ligand, S = substrate, I = intermediate, P = product.
1.2 Proton-Transfer Metal-Ligand Cooperative Complexes
A subset of MLC complexes are proton-transfer (PT) MLC catalysts. These catalysts aid
in formation of product by facilitating proton transfer steps using acidic/basic sites in the
secondary coordination sphere.6,7
Milstein (A), Morris (B), Noyori (C), Gusev (D) among others
have developed complexes capable of performing catalysis in such a manner (Figure 1).8,9,10,11
The acidic/basic sites of these complexes influence catalytic turnover. The ability to easily tune
the electronic properties of these sites without dramatically altering the overall structure of the
ligand may prove to be powerful in catalyst optimization and design.12
L
Lx
M
L
Lx
MS
L
Lx
M I
L
Lx
MP
PL M
L MS
L M I
L MP
SP S
A) B)

11. 2
Figure 1. MLC complexes capable of proton transfer. Basic and acidic sites are respectively shown in blue and red.
1.3 Tunable PR
2NR′
2 Ligands
The 1,5-diaza-3,7-diphosphacyclooctane (PR
2NR′
2) family of ligands contain two
phosphines at the 1,5 position and two amines at the 3,7 position (Figure 2). These eight
membered ring ligands are highly tunable at the R and R′ groups. 7,13,14
This tunability leads to
PR
2NR′
2 emerging as a powerful PT MLC ligand in many electrocatalytic processes. These
ligands have demonstrated the ability to perform, in a cooperative manner, H2 oxidation and
production using Fe15
, Ni16
, and Co17
complexes. These ligands have not yet been used to
perform organic transformations; however the electrocatalytic conversions they have been used
for are analogous to hydrogenation and dehydrogenation chemical reactions.
The R groups attached to the phosphines affect the steric and electronic properties of a
complex predominantly in the primary coordination sphere. Sterically large and/or good electron
donating substituents may hinder a complexes hydride donation ability.13,18,19
For instance
DuBois has demonstrated that the electrocatalyst [Ni(P
Cy
2N
Bz
2)2](BF4)2 is a better hydride
accepting complex than [Ni(P
Ph
2N
Bz
2)2](BF4)2.18
This results in a complex which favors H2
oxidation rather than H2 production, and thus demonstrates the ability to manipulate a reaction by
tuning the R substituent.
Ir
P Ph
H
P(t-Bu)2
H
C
(t-Bu)2
NH
H
Fe
P P
H
N N
CO
H
Ph Ph
Ph2Ph2
Os
CO
H
Cl
N
N
N
P(t-Bu)2
H
H
Morris
B
Milstein
A
Noyori
C
Gusev
D
Ru
N
N
Ph
Ph
H
H
H
Ts

12. 3
Figure 2. a) The structure of the PR
2NR′
2 family of ligand and b) typical coordination of the ligand to a metal center
(M).
The amine groups act as a basic/acidic site to facilitate proton transfer in the secondary
coordination sphere and are affected by the R′ groups. The proton shuttling capabilities of these
sites can therefore be optimized for a particular reaction by modifying the electron donating
properties of the R′ groups. For instance electron withdrawing R′ substituents (i.e. phenyl rather
than benzyl) may hinder protonation at the pendent amine and thus hinder overall catalytic
turnover for a particular reaction.7
This however is not to say a very basic pendent amine is
always more favorable for catalytic processes involving proton-transfer MLC complexes.
Optimal basicity of the amine varies depending on the complexes you are working with and
target reactions.
1.4 Hydration of Terminal Alkynes Using Proton Transfer MLC Catalysts
The anti-Markovnikov hydration of terminal alkynes is a useful method in organic
synthesis for adding aldehydes (and therefore possible functionality) to carbon skeletons.20
Wakatsuki was the first to develop a non-cooperative Ru(II) catalyst capable of performing this
transformation.21
Proton Transfer MLC complexes containing pendent pyridyl and imidizoyl
groups (A and B) were later developed (Figure 3).22,23
The proposed mechanism (Scheme 2) employed by complexes such as A and B of Figure
3 involve coordination of the alkyne to the ruthenium center at an open coordination site,
followed by isomerization to give a ruthenium vinylidene intermediate. Nucleophilic attack by
water will follow, with water showing selectivity for the alpha-carbon. Several proton transfer
steps will facilitate the formation of a Ru-acyl moiety, followed by aldehyde formation and
catalyst regeneration.6,24
Additionally, Complexes such as A and B are deactivated when the
amine groups coordinate to the metal center or to substrate.7
R'N
P
R
NR'
R
P
M
P
P
R
N
N
R
R'
R'
a) b)

13. 4
Figure 3. PT MLC catalysts capable of performing anti-Markovnikov hydration of terminal alkynes.
Scheme 2. Proposed mechanism for the anti-Markovnikov hydration of terminal alkynes using a proton transfer
MLC catalyst: B = Basic site of ligand.
1.5 [Ru(Cp)(PR
2NR’
2)(NCMe)][PF6] In Hydration of Terminal Alkynes
The Blacquiere group has synthesized derivatives of the [Ru(Cp)(PR
2NR'
2)(NCMe)][PF6]
complex where R = Ph or t
Bu and R'
= Bn (Figure 4).6,7
The use of the phenyl and tert-butyl
substituents allow for a comparison in the electron donating properties of the primary
coordination sphere. A previous group member has investigated the ability of complex 1 to
perform the anti-Markovnikov hydration of 1-octyne and phenylacetylene. This was done as a
proof-of-principle reaction to see if the PR
2NR’
2 ligands are capable of such transformations,
however the aldehyde product was not observed. Instead a deactivated complex was generated by
the proximal amine forming a strong Lewis-acid base interaction with the terminal carbon of a
postulated vinylidene intermediate (Scheme 3).6
The deactivation is irreversible and must be
avoided if a productive catalysis is to be achieved. It is speculated that steric protection at the
nitrogen groups and the use of sterically large substrates (i.e. internal alkynes) may prevent this
intramolecular deactivation.6,25
Hintermann
Ru
Ph2P
Ph2P L
N
N
R'
R
N
N
R' R
Grotjahn
Ru
Ph2P
Ph3P L
N
R
BA
R
O
H
R H
H H
[Ru]
[Ru]
C
C
H
R
O
[Ru]
R
H2O
HH
α
βB
H
B
B

14. 5
Figure 4. Derivatives of Ru(Cp)(PR
2NR’
2)(NCMe)][PF6].
Scheme 3. Synthesis of a deactivated through a postulated vinylidene intermediate.6
1.6 [Ru(Cp)(PR
2NR’
2)(NCMe)][PF6] In Acceptorless Dehydrogenation Reactions
Traditional Dehydrogenation reactions require a hydrogen accepting species. Catalysts
capable of performing acceptorless dehydrogenation (AD) do not use an acceptor species because
they are able to produce and release H2 gas. Complexes 1 and 2 are similar in structure to the
[Ru(Cp*)(PR
2NR′
2)(X/L)][PF6] electrocatalyst developed by Bullock and Mayer.6,7,26,27
2 has been shown to be capable performing the AD of benzylamine to produce the
acceptorless dehydrogenation coupling (ADC) product, 1-phenyl-N-(phenylmethyl)-methanimine
(Scheme 4). Conducting this reaction in DMF at 110˚C for 48 h under closed conditions
produced the highest yield.27
1 is also able to perform the AD of benzylamine under the same
conditions, though its overall yield is lower than in reactions with 2. These extreme catalytic
conditions suggests there is a slow step within the catalytic cycle that is limiting turnover.
Scheme 4. The catalytic conversion of benzylamine to give the AD and ADC products.
1.7 Scope of Thesis
The scope of this thesis is to gain a better understanding of complexes 1 and 2 by
investigating important intermediates that are potentially relevant to both hydration and
acceptorless dehydrogenation catalytic cycles. In the case of hydration, we targeted
Ru
P
P
R
N
N
R
R'
R'
PF6
R = Ph, tBu; R' = Bn
Active Catalytic Form
Ru
P
P
NCMePh
N
N
Ph
Bn
Bn
PF6
Ru
P
P
NCMe
tBu
N
N
tBu
Bn
Bn
PF6
21
NH2
Ph
3 mol% [2]
DMF, 48 h, 110 °C
Ph NH + H2 NH3
+Ph N Ph
NH2
Ph

15. 6
stoichiometric reactions with internal alkynes. In the case of AD, we targeted hydride complexes
3 and 4 (Scheme 5). Once synthesized, reactivity studies were performed to give a better
understanding of the catalytic performance of 1 and 2 as governed by the substituents of the
PR
2NR
′ 2 ligand. Dihydrogen species were also targeted for reactivity studies. If H2 release is
facile and occurs readily (Scheme 5) formation of a dihydrogen species should not be favorable
or observed when 1 and 2 are in the presence of H2 gas. Bullock has demonstrated the formation
of a dihydrogen species [Cp*Ru(P
R
2N
Bn
2)H2]BArF
4 (R = Ph, t
Bu) when 1 and 2 analogues,
Cp*Ru(P
R
2N
Bn
2)Cl (R = Ph, t
Bu), are purged with H2 gas at room temperature.26
The ability of a
Cp-phenyl derivative (i.e. complexes 1 or 2) to readily form a dihydrogen species was
investigated.
Scheme 5. Proposed mechanism for the AD of benzylamine using 1 and 2.
2.0 Results and Discussion
2.1 Improved Synthesis of [Ru(Cp)(PtBu
2NBn
2)(NCMe)][PF6]
The synthesis of 1 via the literature procedure is a relatively simple process involving stirring
[Ru(Cp)(η6
-naphthalene)][PF6] in acetonitrile for 72 hours to produce [Ru(Cp)(MeCN)3][PF6].17
The tris(acetonitrile) species may then react with one equivalent of PtBu
2NBn
2 in acetonitrile for 4
hours at 75 ̊C to give 1 in good yield (81%).6
Converting the labile tris(acetonitrile) complex into
Ru
P
P
NCMeR
N
N
R
Bn
Bn
PF6
Ru
P
P
R
N
N
R
Bn
Bn
PF6
Ru
P
P
HR
N
N
R
Bn
Bn
PF6
H
Ru
P
P
R
N
N
R
Bn
Bn
PF6
H
H
-H2
N
PhH
H H
Ph NH
NH3
+
Ph N Ph
NH2
Ph
Ru
P
P
HR
N
N
R
Bn
Bn
+H
3, R = tBu
4, R = Ph
1, R = tBu
2, R = Ph

16. 7
1 requires heat due to the poor solubility of the PtBu
2NBn
2 ligand. An improvement to the literature
synthesis is achieved by combining [Ru(Cp)(MeCN)3][PF6] with PtBu
2NBn
2 in a 1:1 mixture of
acetonitrile and dichloromethane (Scheme 6). Allowing the solution to stir for 20 hours at room
temperature yields 1 in excellent yield (97%). The addition of dichloromethane fully dissolves all
starting material and provides a new method that does not require heat to produce 1 from
[Ru(Cp)(MeCN)3][PF6].
Scheme 6. Improved synthetic route to 1 using a 1:1 mixture of MeCN and DCM for the phosphine ligation.
2.2 Preliminary Stoichiometric Studies of 1 with an Internal Alkyne
Stoichiometric NMR scale reactions were performed to investigate if either a π-bound alkyne, a
vinylammonium or vinylidene complex is formed when 1 is mixed with an internal alkyne
(Scheme 7). Compound 1 was treated with 1.38 equiv of the internal alkyne ethyl
phenylpropiolate in acetone. This alkyne was chosen since it has previously been used in
reactions which give a vinylidene product.28
The reaction was heated to 50˚C for 30 h, after
which the reaction was analyzed by 31
P{1
H} NMR spectroscopy. The 31
P{1
H} NMR spectrum
shows the full consumption of 1. A new set of signals is observed as an AB quartet. The first
doublet of the AB quartet is at 61.4 ppm (J = 64.9 Hz), ca. 6.9 ppm downfield of the singlet for
the starting compound 1 (54.5 ppm). The second doublet is at 60.7 ppm (J = 65.9 Hz), ca. 6.2
ppm downfield of the singlet for the starting compound 1 (Figure 5). The synthesis of the vinyl
ammonium complex that was previously formed on addition of 1 and phenylacetylene (Scheme
3) has a singlet at 71.5 ppm (CDCl3) in the 31
P{1
H} NMR spectrum.6
The location and
multiplicity of the AB quartet is not consistent with the analogous vinyl ammonium. The lack of
mirror plane in the product suggests the species is that of a π-bound alkyne.
Ru Ru
PF6
MeCN
72 h MeCN
MeCN
NCMe
PtBu
2NBn
2
MeCN/DCM
20 h, RT
Ru
P
P
NCMe
tBu
N
N
tBu
Bn
Bn
PF6 PF6
1

17. 8
Scheme 7. Reaction of 1 with an internal alkyne to give possible products: A π-bound alkyne (A), vinylidene (B) or
a vinyl ammonium (C).
Additionally the unknown species appears to begin undergoing decomposition when in
CDCl3 at room temperature for 5 hours due to the formation of many signals in the 31
P{1
H} NMR
(Figure A1). One method of investigating the identity of the unknown species is to conduct
stoichiometric reactions with equal equivalents of water. If the vinylidene was formed there
should be a nuclear attack at C1 or C2, resulting in hydration of the alkyne.
Figure 5. 31
P{1
H} NMR (243 MHz, Acetone) spectra of an unknown species formed when 1 is allowed to react with
ethyl phenylpropiolate.
2.3 Stoichiometric Reactivity Studies of 1 and 2 with H2
Two J. Young tubes containing 1 and 2 in proteo-DMF were degassed and exposed to 1
atm of H2. The tubes were heated (110 °C) and analyzed periodically by 31
P{1
H} NMR
spectroscopy. The reaction conditions were chosen to mimic those for the catalytic ADC of
benzylamine. Over 24 h no consumption of 2 was observed (Figure A3), suggesting H2 binding
to 2 is unfavorable. This result is consistent with the proposed facile H2 release in the catalytic
ADC reactions and eliminates this step as rate-determining in catalysis with 2.
Ru
P
P
NCMe
tBu
N
N
tBu
Bn
Bn
PF6
OEt
O
Ru C1 C2
Ph
EtO
O
N
Bn
Ru
N
Bn
C1 C2
Ph
EtO
O
Acetone,
50 °C, 30 h deactivated vinylammonium
complex
PF6
or
PF6
A B C
1.4 equiv. Ru
N
Bn
PF6
C1
C2
Ph
or
1 EtO
O

18. 9
Scheme 8. Treatment of 1 and 2 with dihydrogen gas.
In contrast to 2, 1 appears to form a dihydrogen species (1-H2) when exposed to H2. At 4
hours, the 31
P{1
H} NMR spectrum shows complete consumption of 1 and the formation of a new
species as identified by a singlet at 60.3 ppm (Figure 6). This species is ca. 5.4 ppm downfield of
1 and integration relative to an internal standard indicates the conversion is quantitative. This
suggests H2 binding to 1 is favorable and thus formation and release of H2 may be limiting
catalytic turnover when complex 1 is used as the catalyst. The ability of 2 to easily release H2
may explain why 2 has greater conversion to the ADC product (99%) than 1 (80%) under the
same conditions.27, 29
Figure 6. 31
P{1
H} NMR spectra (243 MHz, DMF) monitoring the reaction of 1 with H2 at 110 °C: a) 1 (54.9 ppm) at
0 h of H2 exposure, b) 1-H2 (60.3 ppm) at 4 h of H2 exposure, c) 1-H2 (60.3 ppm) at 24 h of H2 exposure.
2.4 Preparation of the Ru-H Complex 3 from 1
NMR scale reactions were conducted to identify the optimal reaction conditions for the synthesis
of Ru(Cp)(H)(PtBu
2NBn
2) (3) using sodium isopropoxide as the hydride donor. The reactions were
performed in THF or acetonitrile at 60˚C or room temperature and the product distribution was
monitored using 31
P{1
H} NMR over the course of 24 hours. In all cases, 31
P{1
H} NMR spectra
Ru
P
P
NCMeR
N
N
R
Bn
Bn
PF6
Ru
P
P
R
N
N
R
Bn
Bn
PF6
H
H1 atm H2+
DMF
110°C
+ MeCN
1, R = tBu
2, R = Ph
1-H2, R = tBu
2-H2, R = Ph

19. 10
revealed no loss of starting material (1) relative to an internal standard (triphenylphosphine
oxide), and the formation of additional peaks was not observed, thus suggesting hydride
installation was unsuccessful.
Sodium borohydride was instead used as the hydride source. Compound 1 was treated
with excess sodium borohydride in THF. The reaction was heated to reflux at 60 ˚C over the
course of 36 hours. An aliquot was withdrawn from the reaction vessel to reveal full consumption
of 1 and the formation of two new signals in the 31
P{1
H} NMR spectrum. Compound 3 is
observed as a singlet at 66.1 ppm, ca. 11.6 ppm downfield of the singlet for the starting
compound 1. An impurity (14% relative to 3) is observed as a singlet at 44.8 ppm, ca. 9.7 ppm
upfield of the singlet for the starting compound 1. Filtration through two successive glass-
microfiber plugs where performed to remove any solid byproducts. Solubility tests found 3, a
yellow residue, to be soluble in hexanes. Extraction of the solid with hexanes proved a successful
method to isolate 3 from the impurity. Grease however could not be removed, as judged by the
1
H NMR. A crude yield of 96% was measured after crystallization (described below). The
product was analyzed by MALDI-MS using anthracene as the matrix. The observed spectrum had
a monoisotopic mass of m/z = 609.2 that differs from the calculated value of m/z = 610.2 for 3
(Figure 7). The simulated values are consistent to the radical molecular cation that results from
hydride fragmentation [CpRu(PtBu
2NBn
2)]+
.
Scheme 9. Synthesis of 3 via hydride transfer.
Ru
P
P
NCMe
tBu
N
N
tBu
Bn
Bn
PF6
Excess NaBH4
THF, 60 °C
+ NaPF6 BH3
36 h
MeCN+
Ru
P
P
H
tBu
N
N
tBu
Bn
Bn
1 3
+ +

20. 11
Figure 7. MALDI-MS analysis of 3 with an anthracene matrix. m/z values are reported in insets with the simulated
spectrum at the top and the experimental spectrum at the bottom.
Vapor diffusion of pentane into a concentrated solution of 3 in THF proved to be
successful in growing pale yellow and orange crystals. 1
H NMR revealed the orange crystals are
3 with minor amounts of grease and residual solvent, and thus are not suitable for X-ray
diffraction analysis. The pale yellow crystals were single crystals amenable to X-ray diffraction
analysis to produce data with an R1 value of 0.0344 (Figure 8). The position of the hydride ligand
was identified from a difference Fourier map, and was allowed to refine isotropically. 1 is a
charge-separated species in which PF6
–
is the anionic component. The absence of PF6
–
from the
unit cell of 3 supports the incorporation of the hydride ligand. Both Ru1
-P1
and Ru1
-P2
have
decreased in 3 from 1. Interestingly the bond angle of P1
-Ru1
-P2
in 3 is very close to that of 1.
Many unsuccessful recrystallizations were attempted to reproduce the pale yellow crystals,
although formation of the orange crystals was often observed.

21. 12
Figure 8. X-ray crystal structure of 3. Thermal ellipsoids are shown at a 50% probability. H1
H indicates the hydride
ligand. Hydrogen atoms and t
Bu groups on the PtBu
2NBn
2 ligand were removed for clarity.
Table 1. Selected bond lengths (Å) and angles (˚) for complexes 1,7
and 3.
Complex P1
-Ru1
P2
-Ru1
P1
-Ru1
-P2
1 2.2868(4) 2.2914(4) 79.643(12)
3 2.2367(5) 2.2370(5) 79.796(16)
The hydride ligand of 3 appears to be not stabile in CDCl3 and MeCN-d3 (Figure 9). When
placed in CDCl3 at room temperature for 48 hours, full conversion of a singlet is observed at 52.4
ppm, ca. 12.4 ppm upfield of the singlet for compound 3 (C6D6). When placed in MeCN-d3 at
room temperature for 48 hours, a singlet is observed at 49.8 ppm, ca. 12.8 ppm upfield of the
singlet for compound 3 in MeCN-d3. A ligand exchange is postulated to have occurred in both
instances to form 5 (in CDCl3) and 1 (MeCN-d3). 3 is stable in C6D6 over 48 hours. As such, to
avoid any competitive decomposition, the characterization of 3 was conducted in C6D6.
1
H NMR spectroscopy was used to confirm the identity of 3. The primary diagnostic
signal for 3 is a triplet at –13.68 ppm (J = 29.6 MHz), which is assigned to the hydride ligand
coupling to both phosphorous atoms of the PtBu
2NBn
2 ligand. The 1
H NMR spectrum of the
analogous Cp* derivative has a diagnostic triplet at –14.94 ppm (J = 31 Hz, C6D6). The
inherently weaker electron donating properties of the Cp ligand supports why the hydride for 3 is
downfield relative the same signal in the Cp* species.

22. 13
Figure 9. 31
P{1
H} NMR spectra (242 MHz) of 3 after 48 hours in the solvents: a) MeCN-d3, where 1 has formed, b)
CDCl3 where 5 has formed, and c) C6D6.
2.5 Preliminary Stoichiometric Preparation of Ru(Cp)(PPh
2NBn
2)(NCMe)(H) Complex 4
from Complex 2
NMR scale reactions using an internal standard were performed in an attempt to synthesis
4 from 2 (Scheme 10). Compound 2 was treated with excess sodium borohydride in THF. The
solution was allowed to stir at 60 ˚C, and was monitored by 31
P{1
H} NMR (Figure 10). After 1.5
h 31
P{1
H} NMR spectroscopy revealed full consumption of 2 and formation of two new signals at
48.1 (s) and 29.8 (s) ppm in an 8:7 ratio. Leaving the reaction for 22 h results in conversion of the
unknown species to compound 4 (1
H NMR described below) giving a 7:1 ratio for the two
species. Additional studies conducted prior to this experiment show the formation of 4 stalls at 22
h. The decomposition of 4 was observed to occur if the reaction time is extended to 72 h. The
assignment of the product as 4 is confirmed by the presence of a triplet signal for the hydride
ligand at –12.57 ppm in the 1
H NMR spectrum (Figure A8). To achieve higher conversion to 4,
without the formation of the unknown byproduct, the reaction was repeated with other reaction
solvents. Attempts to synthesize 4 in ethanol under the same conditions proved unsuccessful.
Isolated synthesis of 4 using a mixture a 1:1 of THF and ethanol are to be investigated.
Ru
P
P
NCMePh
N
N
Ph
Bn
Bn
PF6
Excess NaBH4
THF, 60 °C
+ NaPF6 BH3
22 h
MeCN+
Ru
P
P
HPh
N
N
Ph
Bn
Bn
2 4
+ +

23. 14
Scheme 10. Stoichiometric synthesis of 4 via hydride transfer
Figure 10. 31
P{1
H} NMR spectra (243 MHz) monitoring the stoichiometric formation of 4 (48.1 ppm) from 2 (39.9
ppm): a) 0 h (THF), b) 1.5 h (THF), c) 11 h (THF), d) 22 h (C6D6).
2.6 Preparation of the Ru-H Complex 3 from the Ru-Cl Complex 5
An alternative method of forming 3 is to treat the Ru-Cl complex 5 with NaBH4 to promote
halide abstraction along with hydride transfer (Scheme 11). The chloride abstraction is performed
readily in ethanol by stirring the solution for 4 hours at room temperature. These conditions are
milder than that described above for the synthesis of 3 from 1 (Section 2.2). No heat is required
and the reaction is complete in 4 h, as opposed to 36 hours when 1 is used as the precursor. The
reaction is primarily driven by the formation of NaCl that has a high salt lattice energy. The
product is isolated in excellent yield (92%) with high purity. An impurity in the form of a broad
peak at 1.30 ppm is observed in the 1
H NMR spectrum. This synthetic route initially appears as
an attractive alternative in producing 3 due to its simple and fast reaction conditions. However,
synthesis of the precursor 5 requires a 36 h reaction in which moderate yield is reported and
involves many purification steps.7
Using 1 as a precursor to 3 may therefore be best due to the
resources that must be invested to synthesize 5.

24. 15
Scheme 11. Synthesis of 3 via ligand substitution from 5.
2.7 Stoichiometric Reactivity Studies of Ru-H Complex (3) with Acid Under Closed
Conditions
The proposed mechanism of the ADC of benzylamine (Scheme 5) suggests protonating 3 at the
proximal amine should produce 1 in the presence of acetonitrile. The process occurs by donation
of the proton to the hydride ligand to give 1′-H2 (OTF used as the counterion), followed by
displacement of the H2 ligand by MeCN. This proposal was investigated using 31
P{1
H} and 1
H
NMR spectroscopy following the titration of the acid, [HDMF][OTF] into 3 in CD2Cl2 and with
10.55 equiv. MeCN (Scheme 12).
Scheme 12. Probing the reactivity of 3 with acid in dichloromethane and acetonitrile.
A small amount of 5 (5% relative to 3) is formed when 3 is initially placed in CD2Cl2
(Figure 11). As also shown in Figure 9, 5 is observed due to the instability of 1 in chlorinated
solvents. After 0.2 and 0.4 equiv. of [HDMF][OTF] is added to the solution, the 31
P{1
H} NMR
spectrum shows a broad singlet emerging at 61.6 ppm as the singlet for 3 (64.6 ppm) begins to
decrease in intensity. The singlet for 3 is nearly gone after the addition of 0.6 equiv. of acid. The
integration of the broad signals relative to internal standard reveals no loss of material. At this
point the proximal amine of 3 is postulated to be protonated and facilitating a proton transfer to
the hydride ligand, thus resulting in a ruthenium-dihydrogen complex (1′-H2). The singlet
representative of 1′-H2 has fully emerged after a total of 1.0 equiv. of acid has been added to the
solution. 1′-H2 was assigned to the signal at 51.6 ppm due to diagnostic evidence in the 1
H NMR
spectra, as described below. In addition, the results from the stoichiometric reactions in Section
2.3 show 1-H2 in DMF as a singlet at 60.3 ppm. The 1
H NMR below (Figure 12) will support the
assignment of the 1′-H2 signal as a reasonable one. The full conversion of 1′-H2 to complex 1
Ru
P
P
Cl
tBu
N
N
tBu
Bn
Bn
Excess NaBH4
EtOH, RT
+ NaCl BH3
4 h
+
Ru
P
P
H
tBu
N
N
tBu
Bn
Bn
5 3
+
Ru
P
P
H
tBu
N
N
tBu
Bn
Bn
+ H[DMF][OTF] CD2Cl2
10.55 equiv. MeCN,
RT
Ru
P
P
NCMe
tBu
N
N
tBu
Bn
Bn
OTF
Ru
P
P
R
N
N
R
Bn
Bn
OTF
H
H
3 1'-H2 1'
CD2Cl2
10.55 equiv. MeCN,
RT

25. 16
(52.2 ppm) is observed over 24 hours in CD2Cl2 (Figure 11).
Figure 11. 31
P{1
H} NMR spectra (243 MHz, CD2Cl2) of a) 3; and mixtures of 3 with b) 0.2 equiv [HDMF][OTF]; c)
0.4 equiv [HDMF][OTF]; d) 0.6 equiv [HDMF][OTF]; e) 0.8 equiv [HDMF][OTF], f) 1.0 equiv [HDMF][OTF]; and
g) 1.0 equiv [HDMF][OTF] analyzed after 24 h. Compound 5 is observed as a competitive decomposition product.
In the above titration, micro syringes were used to inject a stock solution of acid (in
CD2Cl2) into the NMR tube containing 3. These injections were performed outside a glove box
and thus, due to difficulties with the micro syringes, the solution is thought to be contaminated
with O2 during the addition of 1.0 total equiv. of acid. Signals at ca. 32.8 and 32.7 ppm (Figure 11
f and g) are attributed to oxidation of the phosphine ligand due to the O2 contaminant. Similar
reactivity studies performed in a glove box (Sections 2.8) do not show the presence of this
species in the 31
P{1
H} NMR.
The acid titration experiment was also analyzed by 1
H NMR spectroscopy. The triplet
resonance for the hydride ligand of 3 at –14.32 ppm shows a decrease in intensity upon the
addition of acid. A diagnostic singlet at –8.64 ppm emerged as equiv. of acid were added to 3
(Figure 12). This is similar to the broad singlet observed at –9.89 ppm for the dihydrogen ligand
of [Cp*Ru(PtBu
2NBn
2)(H2)BArF
4 (CD2Cl2) characterized previously by Bullock.26
The Cp* ligand
is a stronger electron donor than Cp. As such, the singlet for Ru-H2 in 1′-H2 is expected to be
found downfield relative to the Ru-H2 singlet of Bullock’s Cp* analogue.26
This singlet was

26. 17
integrated relative to a methylene peak at 3.91 ppm (Figure A8) to confirm the number of
hydrogen atoms this peak represents. Additionally, conducting the experiment under closed
conditions allowed for the signal of H2 gas to be monitored via 1
H NMR spectroscopy. H2
formation is observed in the reaction mixture as a sharp singlet at 4.60 ppm (Figure 12). Overall,
the postulation that 1 arose from 1′-H2 after 24 h is a reasonable one.
Figure 12. 1
H NMR spectra (599 MHz, CD2Cl2) of a) 3; and mixtures of 3 with b) 0.2 equiv [HDMF][OTF]; c) 0.4
equiv [HDMF][OTF]; d) 0.6 equiv [HDMF][OTF]; e) 0.8 [HDMF][OTF]; f) 1.0 equiv [HDMF][OTF]. The spectra
had a region of peak suppression at 1.90 – 2.00 ppm to remove the large singlet belonging to the methyl hydrogens
of MeCN.
2.8 Stoichiometric Reactivity Studies of Ru(Cp)(PtBu
2NBn
2)(NCMe)(H) with Acid Under
Conditions Allowing for H2 Release From NMR Tube
The protonation of 3 was conducted under open conditions to facilitate the release of generated
gases into the atmosphere. The addition of 0.5 and 1.0 equiv. of [HDMF][OTF] was performed in
a glove box to prevent O2 contamination. Performing the experiment in a glove box also allowed
for the release of H2 from the NMR tube during each addition. MeCN-d3 (8.37 equiv.) was used
instead of MeCN to avoid having to process the 1
H NMR data through peak suppression method.
The reaction was monitored using 31
P{1
H} and 1
H NMR spectroscopy (Figure 13 and A9) after
immediate addition of acid.
A small amount of 5 (3% relative to 3) is formed when 3 is initially placed in CD2Cl2.
After the addition of 0.5 equiv. of [HDMF][OTF], the 31
P{1
H} NMR spectrum shows a broad
singlet for 1′-H2 at 61.9 ppm, ca. 2.4 ppm upfield from 3 (Figure 13). Complete conversion to 1′-

27. 18
H2 is observed after a total of 1.0 equiv. of acid has been added to the solution. Releasing H2 from
the atmosphere of the NMR tube was performed in an attempt to promote H2 dissociation from
the ruthenium metal center to form 1′. This attempt was successful due to the signal for 1′ (52.3
ppm) in the in 31
P{1
H} spectra of Figure 13. This was also done in a glovebox to see if there was
an O2 contamination in section 2.7. The signal at 32.8 ppm assigned as phosphine oxide was not
observed, and thus suggests O2 contamination in Section 2.7 occurred. To confirm if the signal at
52.3 belongs to 1′ as opposed to 5, molar equivalents of 1′ should be injected into the reaction
mixture to see if this peak increases in intensity. The same can be performed with injecting molar
equivalents of 5 to see if this signal increases in intensity or if a new signal emerges.
Figure 13. 31
P{1
H} NMR spectra (243 MHz, CD2Cl2) of a) 3; and mixtures of 3 with b) 0.5 equiv [HDMF][OTF]; c)
1.0 equiv [HDMF][OTF]; and 1.0 equiv [HDMF][OTF] analyzed after 24 h.
3.0 Conclusion
3.1 Compound Synthesis
In summary, combining [Ru(Cp)(MeCN)3][PF6] and PtBu
2NBn
2 in a mixture of dichloromethane
and acetonitrile results in the improved synthesis of [Ru(Cp)(PtBu
2NBn
2)][PF6] 1. A new
ruthenium complex containing a hydride ligand (complex 3) was successfully synthesized from 1,
purified and characterized. An alternative synthesis of 3 is also achieved via halide abstraction of
5. The synthesis of 3 from 5 occurs faster and under milder conditions than 1. However, the
resources required to synthesize and purify 5 suggest 1 is the preferred precursor.

28. 19
The preliminary preparation of complex 4, another ruthenium-hydride complex, was also
investigated. The 1
H NMR spectrum of a reaction mixture shows a diagnostic triplet that is
consistent with the target ruthenium-hydride complex 4. The purity of 4 proved to be poor, as
judged by 31
P{1
H} NMR spectroscopy.
3.2 Stoichiometric Reactivity Studies
The formation of a ruthenium dihydrogen species, 1-H2, is observed by 31
P {1
H} NMR
spectroscopy when 1 is exposed to H2 under catalytic conditions. 2 does not form a dihydrogen
species (2-H2) when exposed to the same conditions. H2 binding to 1 is suggested to be a
favorable process. The difficulty of H2 release from the ruthenium metal center may consequently
be hindering 1’s catalytic performance and thus provides an explanation as to why 2 outperforms
1 during the ADC of benzylamine.
The protonation of 3 under closed conditions in CD2Cl2 and excess acetonitrile was
monitored to see if formation of 1′, 1′-H2, or 5 is observed. Formation of 1′-H2 is gradually
observed as equivalents of acid are added to the solution of 3. This occurs until the addition of
1.0 total equivalents of acid, after which 3 is fully consumed. The identity of 1′-H2 was
confirmed by diagnostic signals in the 1
H NMR. Formation of 1 is observed when 1′-H2 is kept in
CD2Cl2 at room temperature for 24 hours.
4.0 Future Investigations
The reactivity of 3 and [HDMF][OTF] should be monitored in DMF at 110˚C over 48 h (catalytic
conditions) with equivalents of MeCN. This reaction will give insight as to: a) if a dihydrogen
species is observed from 3 under catalytic conditions; b) how fast H2 is released from ruthenium
and; c) if a signal consistent with 1 is observed. If the dihydrogen species is observed the
generation of 1 is postulated to occur due to the presence of MeCN in DMF (a non-coordinating
solvent). An optimal synthesis of 4 should additionally be investigated and scaled-up (100-200
mg) so that these same reactivity studies (as described above) may be performed. As well,
catalysis of 1 and 2 should be investigated to see if activity is dependent on added H2 pressure. A
decrease in performance may suggest regeneration of 1 and 2 is hindered by a slow dissociation
of dihydrogen from ruthenium. Another interesting study would be to protonate the proximal
amine of 1 and conduct reactivity studies with NaBH4 to see if a signal consistent with 1-H2 is
observed (Scheme 13). Overall these proposed reactivity studies may be used to further reinforce

29. 20
the postulated mechanism for the ADC of benzylamine and gain insight as to how these
complexes may be optimized for catalysis.
Scheme 13. A proposed mechanistic study of forming 1-H2.
5.0 Experimental
5.1 General Procedures
All water- and air-sensitive reactions were performed in an inert nitrogen environment using
standard Schlenk or glovebox techniques, unless indicated otherwise. All glassware was oven
dried and cooled under nitrogen atmosphere prior to use. Dry and degassed solvents were
obtained from an Innovative Technology 400-5 Solvent Purification System and stored under a
nitrogen atmosphere over 4 Å molecular sieves. Acetonitrile was not stored over molecular
sieves. Reagents and deuterated solvents were obtained from commercial sources and used
without further purification unless explicitly stated.
All NMR spectra were recorded on a 600 MHz Varian INOVA spectrometer at room
temperature. 31
P{1
H} spectra were referenced externally 85% phosphoric acid at 0.00 ppm.
31
P{1
H} spectra containing triphenylphosphine oxide (O=PPh3) were internally referenced. Peak
multiplicities are designated as: s = singlet, d = doublet, t = triplet, m = multiplet, br = broad.
[CpRu(NCMe)3][PF6] was synthesized by literature procedure17
and stored in a freezer prior to
use. MALDI mass spectrometry data were performed by Kristina Jurcic and collected on an AB
Sciex 5800 TOF/TOF mass spectrometer using anthracene as the matrix in a 20:1 molar ratio to
metal complex. X-ray diffractometry measurements were performed by Dr. Paul Boyle on a
Bruker Kappa Axis Apex2 diffractometer at a temperature of 110 K.
5.1 Preliminary Studies of 1 and Ethyl Phenylpropiolate
In a 4 mL screw-top vial equipped with a magnetic stir bar, 1 (17 mg, 0.021 mmol, 1.00
equiv.) was combined with ethyl phenylpropiolate (5 mg, 0.029 mmol, 1.38 equiv.) in acetone (2
mL). The vial was capped and sealed thoroughly with electrical tape prior to being placed on a
hotplate outside the glove box. The solution stirred for 30 h at 50 ˚C. 31
P{1
H} NMR (243 MHz,
Ru
P
P
NCMe
tBu
N
N
tBu
Bn
Bn
PF6
H
Ru
P
P
H
tBu
N
N
tBu
Bn
Bn
H
PF6
Ru
P
P
tBu
N
N
tBu
Bn
Bn
H
H
PF6
+ NaBH4
1-H2

30. 21
Acetone): δ 61.1(ABq, ∆δAB = 0.7, JAB = 65.9 Hz), -135.7 – -153.4 (m).
5.2 Stoichiometric Reactivity Studies of 1 and 2 with H2
1 (5.0 mg, 0.0065 mmol) and internal standard (O=PPh3) were transferred in a solution of
DMF (1 mL) to a J.Young tube. The J.Young was connected to a Schlenk line equipped with H2.
The N2 atmosphere of the J.Young was removed via freeze, pump, thaw method using a vacuum
connected the Schlenk line. The J.Young was purged three consecutive times with H2 gas (1
atm). At 110 °C, the sealed tube was immersed in an oil bath on a hotplate for 24 h. 31
P{1
H}
NMR (243 MHz, DMF): δ 60.3 (s), 27.1 (s), -125.84 – -154.78 (m). The procedure was repeated
for 2 (4.7 mg, 0.0056 mmol). 31
P{1
H} NMR (243 MHz, DMF): δ 40.83 (s), 27.1 (s), -133.51 – -
156.92 (m).
5.3 Preliminary Stoichiometric Preparation of 4 from 2
In a 4 mL screw-top vial equipped with a magnetic stir bar, 2 (7 mg, 0.008 mmol, 1.00
equiv.) was combined with NaBH4 (4 mg, 0.106 mmol, 13.25 equiv.) and internal standard
(O=PPh3) in 1 mL of THF. The capped vial was thoroughly sealed with electrical tape and
allowed to stir outside of a glovebox for 22 h at 60 ˚C. The color of the solution changed from
orange to light brown. The solvent was removed under vacuum to afford a light brown solid.
Yield (31
P{1
H} NMR spectroscopy): 87%. 31
P{1
H} NMR (243 MHz, C6D6): δ 49.23 (s), 30.18 (s),
25.40 (s).
5.4 Reactivity Studies of 3 and [HDMF][OTF] Under Closed Conditions
A micropipette was used to place 1.000 mL of CD2Cl2 into a 20 mL screw top vial
containing 24 mg of 3. 0.500 mL (3: 12 mg, 0.020 mmol, 1.00 equiv.) of the solution was
withdrawn, combined with internal standard (O=PPh3) and placed in a Wilmad screw-cap NMR
tube. MeCN (0.011 mL, 0.211, 10.55 equiv.) was micropipetted into the NMR tube containing
the solution. CD2Cl2 (1.000 mL) was used to prepare a stock solution of [HDMF][OTF] (0.203 M,
10.15 equiv./mL) in a 4 mL screw-top. The vial was sealed using an autosampler screw thread
cap. Outside a glovebox using a micro syringe, 20 µL (0.20 equiv.) increments of stock solution
was injected into the NMR tube until there was an addition of 100 µL (1.00 equiv.) of acid. The
reaction was monitored by 1
H and 31
P{1
H} NMR after each addition of acid and 24 h after acid
addition. All 1
H spectra had a region of peak suppression at 1.90 – 2.00 ppm to remove the large
singlet belonging to the methyl hydrogens of MeCN.

31. 22
5.5 Reactivity Studies of Ru-H Complex (3) and [HDMF][OTF] Under Open Conditions
Using a micropipette, 1.000 mL of CD2Cl2 was placed into a 20 mL screw-top vial
containing 21 mg of 3. 0.500 mL (containing 3: 10 mg, 0.016 mmol, 1.00 equiv.) of the solution
was withdrawn, combined with internal standard (O=PPh3) and placed in an NMR tube. MeCN-
d3 (0.007 mL, 0.134, 8.37 equiv.) was micro-pipetted into the NMR tube containing the solution.
CD2Cl2 (1.000 mL) was used to prepare a stock solution of [HDMF][OTF] (0.162 M, 10.12
equiv./mL) in a 4 mL screw-top. Inside a glove box using a micro pipette, a total of 0.100 mL
(1.04 equiv.) of stock solution was added to the NMR tube in two 0.500 mL increments. The
reaction was monitored by 1
H and 31
P{1
H} NMR.
5.6 Synthesis of Ru(Cp)(PtBu
2NBn
2)(NCMe)][PF6]
[CpRu(NCMe)3][PF6] was washed washed twelve times using hexanes to remove all
impurities. In a pre-weighed 20 mL screw-top vial equipped with a magnetic stir bar,
[CpRu(NCMe)3][PF6] (177 mg, 0.408 mmol, 1.00 equiv.) was combined with PtBu
2NBn
2 (181 mg,
0.409 mmol, 1.00 equiv.) in a mixture of acetonitrile (10 mL) and dichloromethane (10 mL). The
solution was stirred in a glovebox for 20 h, during which the color of the solution changed from
dark brown to dark orange. The solvent was removed by vacuum to yield a dark orange solid.
Yield: 97% (316 mg, 0.398 mmol). 31
P {1
H} and 1
H NMR spectra matched literature values.6
5.7 Synthesis of Ru(Cp)(PPh
2NBn
2)(NCMe)][PF6]
[CpRu(NCMe)3][PF6] was washed washed twelve times using hexanes to remove all
impurities. In a pre-weighed 20 mL screw-top vial equipped with a magnetic stir bar,
[CpRu(NCMe)3][PF6] (203 mg, 0.467 mmol, 1.00 equiv.) and PPh
2NBn
2 (225 mg, 0.466 mmol,
1.00 equiv.) were combined in a mixture of acetonitrile (10 mL) and dichloromethane (10 mL).
The solution was stirred in a glovebox for 20 h. The color of the solution changed from dark
brown to dark orange.
31
P {1
H} NMR spectra revealed product (2) was made but the reaction did
not go to completion. The solution was transferred to a 100 mL Schlenk flask. The reaction was
heated to reflux and stirred for 18 h on a Schlenk line to drive any unreacted starting material to
completion. In a glovebox, a layer of dark orange crystalline material formed over two weeks
following vapor diffusion of Et2O into a concentration solution of product in acetone. The solvent
was removed under vacuum. Yield: 84% (311 mg, 0.391 mmol). 31
P {1
H} and 1
H NMR spectra
of product matched values obtained through the other synthetic route.30

32. 23
5.8 Synthesis of 3 from 5
NaBH4 (24 mg, 0.634 mmol, 9.61 equiv.) and CpRu(PtBu
2NBn
2)Cl (5) (42 mg, 0.066
mmol, 1 equiv.) were added to two separate 100 ml Schlenk flasks in a glove box. On a Schlenk
line, 10 mL of ethanol was transferred via cannula to the flask containing 5, giving an orange
solution. This orange solution was transferred via cannula to the flask containing NaBH4. The
flask that contained 5 was washed with an additional 10 mL of ethanol to ensure any residual 5
was transferred. Upon transfer, the color of the solution immediately changed from orange to
yellow. The yellow solution was stirred at room temperature for 4 h, during which time the color
of the solution changed to pale yellow. The solvent was removed under vacuum. In a glovebox,
the product (3) was dissolved in hexanes and filtered through two successive glass microfiber
plugs to remove the NaCl byproduct. The filtrate was collected and the solvent was removed
under vacuum to give a pale yellow residue. Yield: 92% (36 mg, 0.060 mmol), purity: 95%. 1
H
NMR (599 MHz, C6D6): δ 7.32 (m, J = 7.4 Hz, 2H, Ar-H), 7.25 (m, J = 7.1 Hz, 2H, Ar-H), 7.16
(m, J = 7.6 Hz, 2H, Ar-H), 7.11 (m, J = 7.6 Hz, 2H, Ar-H), 7.04 (m, J = 23.0, 7.4 Hz, 2H, Ar-H),
4.97 (s, 5H, Cp-H), 3.71 (s, 2H, CH2-Ph), 3.38 (s, 2H, CH2-Ph), 2.98 (dt, J = 9.3, 3.7 Hz, 3H, P-
CH2-N), 2.63 (d, J = 12.7 Hz, 2H, P-CH2-N), 2.39 (d, J = 12.4 Hz, 2H, P-CH2-N), 2.21 (d, J =
11.2 Hz, 2H, P-CH2-N), 0.86 (t, 18H, C(CH3)3), –13.68 (t, J = 29.6 Hz, 1H, Ru-H) ppm. 31
P{1
H}
NMR (243 MHz, C6D6,): δ 64.5 (s). MALDI MS (Anthracene): m/z found 609.2, calcd. [M-H]+
610.2.
5.9 Synthesis of 3 from 1
NaBH4 (84 mg, 2.223 mmol, 13.81 equiv.) and Ru(Cp)(PtBu
2NBn
2)(NCMe)][PF6] (1) (128
mg, 0.161 mmol, 1.00 equiv.) were combined with THF (14 mL) in a 100 mL Schlenk flask
equipped with a magnetic stir bar and a reflux condenser under N2. The solution was heated and
stirred to reflux at 60 ˚C for 36 h. The color of the solution changed from dark to light orange
during the course of the reaction. The product was filtered using benzene and THF through two
successive glass microfiber plugs to remove any solid byproducts and unreacted NaBH4. Hexane
washes were performed in which the filtrate was collected to remove an impurity in the 31
P{1
H}
NMR spectra. The solvent was removed under vacuum to afford an orange solid. Very pale
yellow crystals suitable for X-ray diffraction formed over three weeks following vapor diffusion
of pentane into a concentration solution of the product in THF. The formation of orange crystals
not suitable for diffraction (3 containing grease and residual solvent) is also observed. Both the
pale yellow crystals (pure product) and the orange crystals combine for a crude of 96% (95 mg,

33. 24
0.156 mmol). All NMR data match that of the product reported in 5.9.
6.0 References
1. Atkins, P.W.; Armstrong, F.A.; Hagerman, H.E.; Overton, T.L.; Rourke, J.P.; Weller,
M.T; Shriver & Atkins’ Inorganic Chemistry, 5th
ed.; Oxford University Press: New York
City, New York, 2010.
2. Facts & Figures for the Chemical Industry, Chem. Eng. News, 2009, 87, 33.
3. Trincado, M.; Grützmacher, H., Cooperating Ligands in Catalysis. In Cooperative
Catalysis, Wiley-VCH Verlag GmbH & Co. KGaA: 2015; pp 67-110.
4. Trincado, M.; Grützmacher, H., Cooperating Ligands in Catalysis. In Cooperative
Catalysis, Wiley-VCH Verlag GmbH & Co. KGaA: 2015; pp 67-110.
5. Nebra, N.; Monot, J.; Shaw, R.; Martin-Vaca, B.; Bourissou, D. ACS Catal. 2013, 3,
2930.
6. Bow, J.-P. J.; Boyle, P. D.; Blacquiere, J. M. Eur. J. Inorg. Chem. 2015, 2015, 4162.
7. Tronic, T. A.; Kaminsky, W.; Coggins, M. K.; Mayer, J. M. Inorg. Chem. 2012, 51,
10916.
8. Ben-Ari, E.; Leitus, G.; Shimon, L. J. W.; Milstein, D. J. Am. Chem. Soc. 2006, 128,
15390.
9. Zuo, W.; Lough, A. J.; Li, Y. F.; Morris, R. H. Science 2013, 342, 1080.
10. Haack, K.-J.; Hashiguchi, S.; Fujii, A.; Ikariya, T.; Noyori, R. Angew. Chem. Int. Ed.
Engl. 1997, 36, 285.
11. Spasyuk, D.; Vicent, C.; Gusev, D. G. J. Am. Chem. Soc. 2015, 137, 3743.
12. Rakowski DuBois, M.; DuBois, D. L. Chem. Soc. Rev. 2009, 38, 62.
13. Doud, M. D.; Grice, K. A.; Lilio, A. M.; Seu, C. S.; Kubiak, C. P. Organometallics 2012,
31, 779.
14. Kilgore, U. J.; Stewart, M. P.; Helm, M. L.; Dougherty, W. G.; Kassel, W. S.; DuBois, M.
R.; DuBois, D. L.; Bullock, R. M. Inorg. Chem. 2011, 50, 10908.
15. Liu, T.; Chen, S.; O’Hagan, M. J.; Rakowski DuBois, M.; Bullock, R. M.; DuBois, D. L.
J. Am. Chem. Soc. 2012, 134, 6257.
16. Wilson, A. D.; Shoemaker, R. K.; Miedaner, A.; Muckerman, J. T.; DuBois, D. L.;
DuBois, M. R. Proc. Natl. Acad. Sci. 2007, 104, 6951.
17. Wiedner, E. S.; Yang, J. Y.; Dougherty, W. G.; Kassel, W. S.; Bullock, R. M.; DuBois,

34. 25
M. R.; DuBois, D. L. Organometallics 2010, 29, 5390.
18. Fraze, K.; Wilson, A. D.; Appel, A. M.; DuBois, M. R.; DuBois, D. L. Organometallics
2007, 26, 3918.
19. Yang, J. Y.; Chen, S.; Dougherty, W. G.; Kassel, W. S.; Bullock, R. M.; DuBois, D. L.;
Raugei, S.; Rousseau, R.; Dupuis, M.; DuBois, M. R. Chem. Commun. 2010, 46, 8618.
20. M. Beller, J. Seayad, A. Tillack, H. Jiao, Angew. Chem. 2004, 116, 3448 – 3479; Angew.
Chem. Int. Ed. 2004, 43, 3368 – 3398.
21. Tokunaga, M.; Wakatsuki, Y. Angew. Chem. Int. Ed. 1998, 37, 2867.
22. Grotjahn, D. B.; Lev, D. A. J. Am. Chem. Soc. 2004, 126, 12232.
23. Boeck, F.; Kribber, T.; Xiao, L.; Hintermann, L. J. Am. Chem. Soc. 2011, 133, 8138.
24. Grotjahn, D. B.; Incarvito, C. D.; Rheingold, A. L. Angew. Chem. Int. Ed. 2001, 40, 3884.
25. D. B. Grotjahn, V. Miranda-Soto, E. J. Kragulj, D. A. Lev, G. Erdogan, X. Zeng, A. L.
Cooksy, J. Am. Chem. Soc. 2008, 130, 20–21.
26. Liu, T.; DuBois, M. R.; DuBois, D. L.; Bullock, R. M. Energy Environ. Sci. 2014, 7,
3630.
27. Stubbs, J. PhD. First Year Report, Western University, 2015.
28. E.; de los Ríos, I.; Macías-Arce, I.; Puerta, M. C.; Valerga, P.; Ortuño, M. Á.; Ujaque, G.;
Lledós, A. Organometallics 2011, 30, 4014
29. Davenport, S. BSc. Dissertation, Western University, 2016.
30. James M. Stubbs, John-Paul J. Bow and Johanna M. Blacquiere, Manuscript in
Preparation.

35. A
7.0 Appendix
7.1 NMR Spectra
Figure A1. 31
P{1
H} NMR (243 MHz, CDCl3) spectra when the unknown species in Section 2.2 is left in
CDCl3 at room temperature for 5 hours.

36. B
Figure A2. 31
P{1
H} NMR (243 MHz) spectra monitoring the purification of 3 in Scheme 7: a) 3 (66.1
ppm) and an impurity (44.8 ppm) in THF, b) isolation of 3 (65.2 ppm, C6D6) after hexane washes were
performed in which the filtrate was collected

37. C
Figure A3. 31
P{1
H} NMR spectra (243 MHz, DMF) monitoring the ability of 2 to form 2-H2 when
exposed to H2 in DMF at 110 °C: a) 2 (41.4 ppm) at 0 h of H2 exposure, b) 2 (40.8 ppm) at 4 h of H2
exposure, c) 2 (40.8 ppm) at 24 h of H2 exposure

38. D
Figure A4. 31
P{1
H} NMR spectra of 3 (243 MHz, C6D6)
Figure A5. 1
H NMR spectra of 3 (599 MHz, C6D6)

39. E
Figure A6. 1
H NMR spectra (599 MHz, CD2Cl2) of 1′-H2 after addition of 0.8 equiv. of [HDMF][OTF].
Integration of known peaks are included to confirm the number of peaks belonging to the diagnostic Ru-H2
singlet. The spectrum had a region of peak suppression at 1.90 - 2.00 ppm to remove the large singlet
belonging to the methyl hydrogens of MeCN
Figure A7. 1
H NMR spectra (599 MHz, CD2Cl2) qualitatively showing the formation of 1′-H2 after
addition of 1.0 equiv. of [HDMF][OTF]. Integration of known peaks are included to confirm the number of
peaks belonging to the diagnostic Ru-H2 singlet. The spectra had a region of peak suppression at 1.90 - 2.00
ppm to remove the large singlet belonging to the methyl hydrogens of MeCN

40. F
Figure A8. 1
H NMR spectra (599 MHz, C6D6) of 4 highlighting the diagnostic triplet at –12.57 ppm.
Figure A9. 1
H NMR spectra (599 MHz, CD2Cl2) monitoring the formation Ru-H2 in 1′-H2 (–8.49 ppm)

41. G
after x.x equiv. of [HDMF][OTF] are added to a solution of 3: a) addition of 0.0 equiv., b) addition of 0.5
equiv., c) addition of 1.0 equiv., d) 24 h after addition of acid

42. H
7.2 X-Ray Diffraction Crystallography Data
Experimental for 3 (C31H46N2P2Ru)
Data Collection and Processing. The sample 3 was submitted by Elias El-Zouki of the
Blacquiere research group at the University of Western Ontario. The sample was
mounted on a Mitegen polyimide micromount with a small amount of Paratone N oil. All
X-ray measurements were made on a Bruker Kappa Axis Apex2 diffractometer at a
temperature of 110 K. The unit cell dimensions were determined from a symmetry
constrained fit of 9360 reflections with 5.78° < 2q < 69.38°. The data collection strategy
was a number of w and j scans which collected data up to 70.152° (2q). The frame
integration was performed using SAINT.1
The resulting raw data was scaled and
absorption corrected using a multi-scan averaging of symmetry equivalent data using
SADABS.2
Structure Solution and Refinement. The structure was solved by using a dual space
methodology using the SHELXT program.3
All non-hydrogen atoms were obtained from
the initial solution. The carbon bound hydrogen atoms were introduced at idealized
positions and were allowed to ride on the parent atom. The hydride ligand's position was
obtained from a difference Fourier map, and was allowed to refine isotropically. The
structural model was fit to the data using full matrix least-squares based on F2. The
calculated structure factors included corrections for anomalous dispersion from the usual
tabulation. The structure was refined using the SHELXL-2014 program from the
SHELXTL suite of crystallographic software.4
Graphic plots were produced using the
NRCVAX program suite.5
Additional information and other relevant literature references
can be found in the reference section of this website (http://xray.chem.uwo.ca).

43. I
Figure 1. ORTEP drawing of 3 showing naming and numbering scheme. Ellipsoids are
at the 50% probability level. The hydride hydrogen atom was drawn with an arbitrary
radius for clarity; the remaining hydrogen atoms were omitted for clarity.
___________________________
1. Bruker-AXS, SAINT version 2013.8, 2013, Bruker-AXS, Madison, WI 53711, USA
2. Bruker-AXS, SADABS version 2012.1, 2012, Bruker-AXS, Madison, WI 53711, USA
3. Sheldrick, G. M., Acta Cryst. 2015, A71, 3-8
4. Sheldrick, G. M., Acta Cryst. 2015, C71, 3-8
5. Gabe, E. J.; Le Page, Y.; Charland, J. P.; Lee, F. L. and White, P. S. J. Appl. Cryst.
1989, 22, 384-387
Table 1. Summary of Crystal Data for 3
Formula C31H46N2P2Ru
Formula Weight (g/mol) 609.71
Crystal Dimensions (mm ) 0.235 × 0.179 × 0.041
Crystal Color and Habit yellow prism
Crystal System monoclinic
Space Group P 21/c

44. J
Temperature, K 110
a, Å 11.001(2)
b, Å 31.506(7)
c, Å 8.6289(17)
α,° 90
β,° 97.894(10)
γ,° 90
V, Å3
2962.5(10)
Number of reflections to determine final unit cell 9360
Min and Max 2θ for cell determination, ° 5.78, 69.38
Z 4
F(000) 1280
ρ (g/cm) 1.367
λ, Å, (MoKα) 0.71073
µ, (cm-1
) 0.660
Diffractometer Type Bruker Kappa Axis Apex2
Scan Type(s) phi and omega scans
Max 2θ for data collection, ° 70.152
Measured fraction of data 0.998
Number of reflections measured 116761
Unique reflections measured 12925
Rmerge 0.0528
Number of reflections included in refinement 12925
Cut off Threshold Expression I > 2sigma(I)
Structure refined using full matrix least-squares using F2
Weighting Scheme w=1/[sigma2
(Fo2
)+(0.0287P)2
+1.5696
P] where P=(Fo2
+2Fc2
)/3
Number of parameters in least-squares 335
R1 0.0344
wR2 0.0704
R1 (all data) 0.0458
wR2 (all data) 0.0742
GOF 1.049

45. K
Maximum shift/error 0.004
Min & Max peak heights on final ΔF Map (e-
/Å) -0.897, 0.737
Where:
R1 = Σ( |Fo| - |Fc| ) / Σ Fo
wR2 = [ Σ( w( Fo
2
- Fc
2
)2
) / Σ(w Fo
4
) ]½
GOF = [ Σ( w( Fo
2
- Fc
2
)2
) / (No. of reflns. - No. of params. ) ]½