The document summarizes the synthesis and characterization of two new organometallic complexes: (1) (dppe)Pt(TeFc)2, a platinum complex with two ferrocenyltelluride ligands, and (2) (dppe)Pt(μ-TeFc)2Re(CO)3Cl, a mixed-metal complex formed from complex 1 chelating to a rhenium fragment. Both complexes were characterized using X-ray crystallography, NMR spectroscopy, and electrochemical measurements. The molecular structures show square planar platinum centers bound to tellurium, with shorter Pt-Te bonds than expected, indicating dative bonding interactions. Electrochemical studies revealed multiple
Computer-assisted study on the reaction between pyruvate and ylide in the pat...Omar Alvarardo
n this study the formation of the lactyl–thia-
min diphosphate intermediate (L–ThDP) is addressed using
density functional theory calculations at X3LYP/6-
31??G(d,p) level of theory. The study includes potential
energy surface scans, transition state search, and intrinsic
reaction coordinate calculations. Reactivity is analyzed in
terms of Fukui functions. The results allow to conclude that
the reaction leading to the formation of L–ThDP occurs via
a concerted mechanism, and during the nucleophilic attack
on the pyruvate molecule, the ylide is in its AP form. The
calculated activation barrier for the reaction is 19.2 kcal/
mol, in agreement with the experimental reported value.
Preparation characterization and conductivity studies of Nasicon systems Ag3-...iosrjce
Materials belonging to NASICON family of compositions Ag3-2xTaxIn2-x(PO4)3 ( x = 0.6,0.8 and 1.1)
are prepared by sol-gel method. Ethylene glycol is used as a gelating agent. All the compositions are
characterizedby powder X-ray diffraction and Fourier transform infrared spectroscopy All these
phosphates are crystallized in rhombohedral lattice with space group R3c
. These compounds exhibit
characteristic PO4 vibrational modes in their FT-IR spectra. The dc conductivity of Ag3-2xTaxIn2-x(PO4)3 ( x =
0.6,0.8 and 1.1) was also investigated.
Computer-assisted study on the reaction between pyruvate and ylide in the pat...Omar Alvarardo
n this study the formation of the lactyl–thia-
min diphosphate intermediate (L–ThDP) is addressed using
density functional theory calculations at X3LYP/6-
31??G(d,p) level of theory. The study includes potential
energy surface scans, transition state search, and intrinsic
reaction coordinate calculations. Reactivity is analyzed in
terms of Fukui functions. The results allow to conclude that
the reaction leading to the formation of L–ThDP occurs via
a concerted mechanism, and during the nucleophilic attack
on the pyruvate molecule, the ylide is in its AP form. The
calculated activation barrier for the reaction is 19.2 kcal/
mol, in agreement with the experimental reported value.
Preparation characterization and conductivity studies of Nasicon systems Ag3-...iosrjce
Materials belonging to NASICON family of compositions Ag3-2xTaxIn2-x(PO4)3 ( x = 0.6,0.8 and 1.1)
are prepared by sol-gel method. Ethylene glycol is used as a gelating agent. All the compositions are
characterizedby powder X-ray diffraction and Fourier transform infrared spectroscopy All these
phosphates are crystallized in rhombohedral lattice with space group R3c
. These compounds exhibit
characteristic PO4 vibrational modes in their FT-IR spectra. The dc conductivity of Ag3-2xTaxIn2-x(PO4)3 ( x =
0.6,0.8 and 1.1) was also investigated.
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Definition - Mechanism - Effect of dielectric constant on the rate of reactions in solutions - Salt effect - Primary salt effect - Bronsted – Bjerrum equation - Secondary salt effect - Effect of pressure on rate of reaction in solution - Volume of activation - Significance
Properties of coordination compoundes part 1 of 3Chris Sonntag
Applications of Crystal Field Theory to explain physical properties of coordination compounds, such as color, lattice energy, hydration energy and Spinel types
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Definition - Mechanism - Effect of dielectric constant on the rate of reactions in solutions - Salt effect - Primary salt effect - Bronsted – Bjerrum equation - Secondary salt effect - Effect of pressure on rate of reaction in solution - Volume of activation - Significance
Properties of coordination compoundes part 1 of 3Chris Sonntag
Applications of Crystal Field Theory to explain physical properties of coordination compounds, such as color, lattice energy, hydration energy and Spinel types
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Hasta un 75% del desgaste del motor ocurre durante el calentamiento. Cuando el motor está apagado, el aceite drena despegándose de las partes críticas del motor, sin embargo, Castrol Magnatec 15W-40 con sus Moléculas Inteligentes no se desprenden, se adhieren como un imán proporcionando una capa de protección adicional, lista para proteger desde que gira la llave.
Las Moléculas de Castrol Magnatec están siempre listas para proteger reduciendo
dramáticamente el desgaste del motor durante el calentamiento cuando ocurre la
mayor parte del desgaste.
Sus Moléculas Inteligentes brindan protección que ahora puede ver, tocar o sentir.
Castrol Magnatec, protección desde que gira la llave.
Hasta un 75% del desgaste del motor ocurre durante el calentamiento. Cuando el motor está apagado, el aceite drena despegándose de las partes críticas del motor, sin embargo, Castrol Magnatec 20W-50 con sus Moléculas Inteligentes no se desprenden, se adhieren como un imán proporcionando una capa de protección adicional, lista para proteger desde que gira la llave.
Las Moléculas de Castrol Magnatec están siempre listas para proteger
reduciendo dramáticamente el desgaste* del motor durante el calentamiento que es cuando ocurre la mayor parte del desgaste.
Sus Moléculas Inteligentes brindan protección que ahora puede ver, tocar o sentir.
Castrol Magnatec, protección desde que gira la llave.
Hasta un 75% del desgaste del motor ocurre durante el calentamiento.
Cuando el motor está apagado, el aceite drena despegándose de las partes críticas del motor, sin embargo, Castrol Magnatec 10W-40 con sus Moléculas Inteligentes no se desprenden, se adhieren como un imán proporcionando una capa de protección adicional, lista para proteger desde que gira la llave.
Las Moléculas de Castrol Magnatec están siempre listas para proteger reduciendo dramáticamente el desgaste* del motor durante el calentamiento cuando ocurre la mayor parte del desgaste.
Sus Moléculas Inteligentes brindan protección que ahora puede ver, tocar o sentir.
Castrol Magnatec, protección desde que gira la llave.
Synthesis, Physicochemical Characterization and Structure Determination of So...IOSR Journals
Some novel nickel(II) complexes with the ligand (z)-4-((2-hydroxy-3-
methoxyphenyl)diazenyl)-1,5-dimethyl-2-phenyl-1H-pyrazol-3-(2H)-one,GAAP,guiacolazoantipyrine, L
having molecular formulae [Ni(L)2X2] and [Ni(L)2(NCS)Cl] where X = Cl-, Br-, NO3
- were synthesized and
characterized. The elemental analysis, Spectral (IR, UV-Visible, EPR, FAB – mass) studies and thermo
gravimetric analysis reveals that the Ni(II) is six coordinated in its complexes. A rhombic symmetry can be
tentatively proposed for the complexes. The magnetic susceptibility measurements show that the complexes are
paramagnetic in nature. The powder XRD study shows its anisotropic nature
Four new trinuclear Fe(III) complexes involving tetradenta Schiff bases N,N1-bis(salicylidene) ethylenediamine-
(salenH2) or bis(salicylidene)-o-phenylenediamine-(salophH2) with 2,4,6-tris(2,5-dicarboxyphenylimino-4-formylphenoxy)-
1,3,5-triazine (DCPI-TRIPOD) or 2,4,6-tris(4-carboxyphenylimino-4¢-formylphenoxy)-1,3,5-triazine
(CPI-TRIPOD) have been synthesized and characterized by means of elemental analysis carrying out 1H-n.m.r., i.r.
spectroscopy, thermal analyses and magnetic susceptibility measurements. The complexes can also be characterized
as high-spin distorted octahedral FeIII bridged by carboxylic acids. The tricarboxylic acids play a role as bridges for
weak antiferromagnetic intramolecular exchange.
Alkali P-Nitrophenolates for Short Wavelength Laser GenerationEditor IJCATR
Single crystals of alkali p-Nitrophenolates namely sodium p-nitrophenolate dihydrate (SPNP), potassium p- nitrophenolate
monohydrate (PPNP) and lithium p-nitrophenolate trihydrate (LPNP) using Group I elements (Na, K, Li) and p-nitrophenols were grown
by solvent evaporation method. Single crystal XRD analysis shows that SPNP and LPNP crystallize in noncentrosymmetric space group
while PPNP is centrosymmetric. Using Autox software, all the peaks in the recorded powder XRD spectrum of the samples were identified
and indexed. The FT – IR spectra of the sample reveals the characteristic vibrations of the functional groups present in alkalinitrophenolates.
A weak absorption band around the region 1589–1641 cm-1 confirms the presence of the phenolic ring. A broad
intermolecular hydrogen bonded OH stretching at 3325 cm-1 of p- nitrophenol is shifted which shows the increase in the polarizable nature
of p–nitrophenol and thus easily forms a metal (sodium/ potassium/ lithium) coordination compound. UV-Vis spectrum shows that all the
crystals are transparent above 400 nm and has a wide optical window in the visible region. Intense absorption peak in the UV region may
be due to the colored nature of the compound. Addition of metal ion (sodium/potassium) modifies the optical transparency of the original
molecule (p-nitro phenol) and consequently introduces a bath chromic shift of 90/40 nm in the crystal transparency of the samples. Kurtz
powder technique result shows that the relative SHG efficiency of SPNP and LPNP was nearly 5 and 9.25 times of KDP.
Synthesis and Crystal Structure of Anickel (II) and Zinc (II) Complex From 1,...IOSRJAC
:The title mononuclear nickel and zinc complexes, Ni(C11H9N4S3)2andZn(C11H9N4S3)2 .2(C3H7NO), were prepared by the reaction of Nickel(II) or Zinc(II)acetate with 1,5-bis[(2- thiophenyl)methylidene]thiocarbonohydrazide in a methanol solution. It features mono-deprotonated bisbidentate ligands, which coordinate to metal (II) ions by hydrazylN and thiocarbony lS atoms, yielding a tetracoordinated metal ions complexes. In Ni(II) complex the geometry around the metal ion is described as square planar. In the Zn(II) the metal atom shows severely tetrahedral distortion from anideal square-planar coordination geometry, as reflected by the dihedral angle between ZnN2and ZnS2 planes of 73.03(13)°. Two intramolecular hydrogen bonds are observed between the solvate dmf molecules and the coordinated ligands:N2—H2N…O1i and N6—H6N…O2 ii in this complex
Spectral studies of 5-({4-amino-2-[(Z)-(2-hydroxybenzylidene) amino] pyrimidi...IOSR Journals
Some transition metal ions Complexes with 5-({4-amino-2-[(Z)-(2-hydroxybenzylidene) amino]
pyrimidin-5-yl} methyl)-2,3,4-trimethoxybenzene were prepared and characterized by elemental analyses,
Infrared , magnetic moment, electronic spectra , mass spectra, X-ray powder diffraction, molar conductance
and thermal analysis (TGA). The complexes have general formulae [ML2.2H2O] {where M = Mn (II), Co (II), Ni
(II), Cu (II), Zn (II), Pd (II) and Pt (II). The coordination behavior of the metal ions towards to the investigated
Schiff base takes place through –C=N,-NH2 and –OH groups. The obtained C, H and N elemental analysis data
showed the Metal: Ligand ratio is 1:2 [M: L] ratio. The molar conductance data reveal that all the metal
complexes are non-electrolytic in nature. From the magnetic moments the complexes are paramagnetic except
Zn metal ion complexes have octahedral geometry with coordination number eight. The thermal behavior of
these complexes shows that, the hydrated complexes have loses two water molecules and immediately followed
by decomposition of the anions and ligand molecules in the second and third stage. The Schiff bases and metal
complexes show good activity against some bacteria. The antimicrobial results indicate that, the metal
complexes have better antimicrobial activity as compared to the prepared Schiff base.
ZEISES SALT - KPtCl3(C 2 H 4) Paper #3November 18,.docxdanielfoster65629
ZEISE'S SALT - KPtCl3(C 2 H 4) Paper #3
November 18, 2014
ZEISE'S SALT - KPtCl3(C 2 H 4) Paper #3
November 18, 2014
ZEISE'S SALT - KPtCl3(C 2 H 4)
This is the first metal complex identified as an organometallic compound KPtCl3(C 2 H 4) obtained from reaction of ethylene with platinum (II) chloride by William Zeise in 1825. It was not until much later (1951–1952) that the correct structure of Zeise's compound was reported in connection with the structure of a metallocene compound known as ferrocene. The anion of this air-stable, yellow, coordination complex contains an η2-ethylene ligand and features a platinum atom with a square planar geometry. Zeise's salt is of historical importance in the area of organometallic chemistry as one of the first examples of an alkene complex and that is the major reason for selecting this title.
INTRODUCTION
Inorganic chemistry is the study of the synthesis and behaviour of inorganic and organometallic compounds. This field covers all chemical compounds except the myriad organic compounds (carbon based compounds, usually containing C-H bonds), which are the subjects of organic chemistry.
Organometallic compounds are considered to contain the M-C-H group. The metal (M) in these species can either be a main group element or a transition metal. Operationally, the definition of an organometallic compound is more relaxed to include also highly lipophilic complexes such as metal carbonyls and even metal alkoxides.
In organometallic compounds, most p-electrons of transition metals conform to an empirical rule called the 18-electron rule. This rule assumes that the metal atom accepts from its ligands the number of electrons needed in order for it to attain the electronic configuration of the next noble gas. It assumes that the valence shells of the metal atom will contain 18 electrons. Thus, the sum of the number of d electrons plus the number of electrons supplied by the ligands will be 18. Ferrocene, for example, has 6 d electrons from Fe(II), plus 2 × 6 electrons from the two 5-membered rings, for a total of 18.
Zeise's salt is a coordination compound, K+ ion and water molecule is present outside the coordination sphere. Both, the Cl-ion and ethylene are coordinated with Platinum ion, hence inside the coordination sphere. Molecular formula of the salt is given as K[PtCl3(C2H4)]·H2O
ZEISE'S SALT PREPARATION
W. C. Zeise, a professor at the University of Copenhagen was the first person to prepare zeise’s salt, he prepared this compound in 1820s while investigating the reaction of PtCl4 with boiling ethanol, and proposed that the resulting compound contained ethylene. in 1868 Birnbaum prepared the complex using ethylene. Zeise’s salt compound is now commercially available as a hydrate. Hydrates are inorganic salts "containing water molecules combined in a definite ratio as an integral part of the crystal that are either bound to a metal center or that have crystallized with the metal .
Highly Crystalline Surface Supported Metal Organic Thin Film Materials Based ...CrimsonpublishersPRSP
Highly Crystalline Surface Supported Metal Organic Thin Film Materials Based Heterojunctions for Triplet-Triplet Annihilation Upconversion by Shargeel Ahmad* in Peer Review Journal of Solar & Photoenergy Systems
Spectroscopic and Thermal Characterization of Charge-Transfer Complexes Forme...IJMER
The spectrophotometric characteristics of the solid charge-transfer molecular complexes
(CT) formed in the reaction of the electron donor 2-amino-6-ethylpyridine (2A6EPy) with the π-
acceptors tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and 2,4,4,6-
tetrabromo-2,5-cyclohexadienone (TBCHD) have been studied in chloroform at 25 0C. These were
investigated through electronic, infrared, mass spectra and thermal studies as well as elemental
analysis. The results show that the formed solid CT- complexes have the formulas [(2A6EPy)(TCNE)2],
[(2A6EPy)2(DDQ)], [(2A6EPy)4(TBCHD)] for 2-amino-6-ethylpyridine in full agreement with the
known reaction stoichiometries in solution as well as the elemental measurements. The formation
constant kCT, molar extinction coefficient εCT, free energy change ∆G
0
and CT energy ECT have been
calculated for the CT- complexes [(2A6EPy)(TCNE)2], [(2A6EPy)2(DDQ)].
Spectroscopic and Thermal Characterization of Charge-Transfer Complexes Forme...
10.1007@s10876-014-0767-4
1. ORIGINAL PAPER
Synthesis and Molecular Structure of Redox Active
Platinum–Bis(Telluroferrocenyl) Complex and its
Chelated Rhenium-Chloro(Tricarbonyl) Derivative
Alexander A. Pasynskii • Yury V. Torubaev •
Alina Pavlova • Ivan V. Skabitsky • Gleb Denisov •
Vitaly A. Grinberg
Received: 17 April 2014
Ó Springer Science+Business Media New York 2014
Abstract A new chelating metalloligand (dppe)Pt(TeFc)2 (Fc = ferrocenyl) (1)
was synthesized and used to prepare a mixed-metal tellurate-brigded complex
(dppe)Pt(l-TeFc)2Re(CO)3Cl (2). Both compounds were structurally and electro-
chemically investigated. Details of their molecular structure and CVA are discussed.
Keywords Mixed-metal complexes Á Cluster Á Ferrocenyltelluride Á Platinum Á
Rhenium Á Electrochemistry Á X-ray analyses
Introduction
Chelating metalloligands proved to be efficient as a ‘‘building blocks’’ in the
targeted fabrication of mixed-metal clusters. In contrast to a vast number platinum-
sulfide clusters [1] and thiolate-chelates there are just a few structural reports of
Pt-organotellurium mixed metal complexes [2] where Pt atom usually appeared as a
chelated metal center (Scheme 1a), but not as a part of a chelating metalloligand.
Electronic supplementary material The online version of this article (doi:10.1007/s10876-014-0767-4)
contains supplementary material, which is available to authorized users.
A. A. Pasynskii Á Y. V. Torubaev (&) Á A. Pavlova Á I. V. Skabitsky
N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, GSP-1,
Leninsky Prospect, 31, 119991 Moscow, Russia
e-mail: torubaev@igic.ras.ru
G. Denisov
Higher Chemical College of Russian Academy of Sciences, Miusskaya Sq. 9, 125047 Moscow,
Russia
V. A. Grinberg
A.N.Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
GSP-1, Leninsky Prospect, 31, 119991 Moscow, Russia
123
J Clust Sci
DOI 10.1007/s10876-014-0767-4
2. Recently we have synthesized platinum(II) bis-tellurophenolate (dppe)Pt(TePh)2
and investigated its chelating ability [3] (Scheme 1b).
The replacement of aryl group with the ferrocenyl fragment genereates new
redox active sites in the molecule, increases electron density on chalcogen atom and
can stabilize the electron-deficient complexes [4].
As a part of our ongoing project for the targeted preparation of the mixed-metal
chalcogenide clusters, we have prepared Pt-bis(telluroferrocenyl) complex
(dppe)Pt(FcTe)2 (1) and used it as a chelating metalloligand to synthesize mixed-
metal cluster (dppe)Pt(l-TeFc)2Re(CO)3Cl (2). The presence of two ferrocenyl
groups in each molecule gave interesting opportunity to investigate the electro-
chemical properties.
Results and Discussion
Synthesis
The starting complex 1 was synthesized by analogy with its known congeners in the
reaction of appropriate Pt-dichloride complex with telluroferrocenyl anion generated
in situ. Complex 1 was isolated as air-stable yellow-orange crystalline substance. Its
further treatment with one equivalent of Re(CO)5Cl in boiling toluene allowed the
complex 2—the product of (CO)3ReCl chelation with 1 (Scheme 2) in a form of
yellow-orange crystals.
Ir
Te
Te
Tol
Tol
Cp*
OC
Ir
Te
Te
Tol
Tol
Cp*
OC
PtCl2
(COD)PtCl2
P
Pt
P Te
Te
Ph
Ph
Ph Ph
Ph Ph
P
Pt
P
Te
Te
Ph
Ph
Ph Ph
Ph Ph
[Re(CO)4(µ-Cl)]2
Re(CO)3Cl
(a)
(b)
Scheme 1 Pt as a chelated metal-center (a) and a part of chelating metalloligand ligand (b)
A. A. Pasynskii et al.
123
3. Molecular Structure
The ferrocenyl groups of two cis-TeFc ligands in complex 1 are diverted from one
another in the same fashion as the phenyl groups in (dppe)Pt(TePh)2 [5] and the
cymantrenyl groups in (PPh3)2Pt(SC5H4Mn(CO)3)2 [6]. The pronounced deviation
of Te atom from the plane of the related Cp ring to Fe atom takes place (av. 7°) is
not as deep as (20.3°) observed in [FcTe–TeCl2Fc] [7]. But may result from the
same Fc ? Te dative interaction.
An average interatomic distances Pt-Te in the square-planar coordination
surrounding of Pt center in the molecules 1 (2.62 A˚´
) and 2 (2.65 A˚´
) are within the
range, normally observed in the similar [P]2Pt(TeR)2 complexes [5, 8] but Pt-Te and
Re-Te distances are shorter than the sum of appropriate covalent radii (2.74 and 2.89
A respectively) [9] as a result of dative M ? Te interaction of M lone pare with
vacant orbitals of Te ligand [10] (Figs. 1, 2).
NMR Spectroscopy
1
H NMR spectra of 1 is consistent with its solid state structure. 31
P spectra shows
typical picture for two equivalent phosphines coordinated to the platinum atom,
1
JPt–P coupling constant 2,848 Hz is similar to TePh analogue (2,896 Hz) [5]. 125
Te
signal appears as triplet, possibly due to accidental coincidence of 2
JTe-P (59 Hz)
coupling constants with cis and trans phosphorous atom.
In 1
H spectra of 2 the signals of protons of tellurium-substituted cyclopentadienyl
rings are shifted downfield, possibly as result of electron density withdrawing from
Te atoms at their coordination to rhenium.
1
H NMR spectra of 2 is consistent with anti-arrangement of ferrocenyl groups,
revealed by XRD, showing eight broad apparent singlets of diastereotopic
protons of two nonequivalent TeC5H4 fragmets and two singlets for nonequiv-
alent C5H5 fragments. The broadening of signals could be attributed to inversion
at tellurium atoms or Cl/CO ligands position exchange at rhenium making two
ferrocenyl groups equivalent. The signals of nonequivalent 31
P nuclei at 40.5
(1
JPt–P 2,967 Hz) and 37.4 ppm (1
JPt–P 2,797 Hz) are also broaden due to the
same dynamic process and 2
JP-P coupling constant and 125
Te satellites could not
be observed.
P
Pt
P Te
Te
Fc
Fc
Ph Ph
Ph Ph
P
Pt
P Te
Te
Fc
Fc
Ph Ph
Ph Ph
Re(CO)3Cl
P
PtCl2
P
Ph Ph
Ph Ph
FcTeNa Re(CO)5Cl
Scheme 2 Formation of 1 and 2
Redox Active Platinum–Bis(Telluroferrocenyl) Complex
123
4. Electrochemistry
In the case of complex 1 the irreversible of one-electron oxidation wave at 0.24 V
(Fig. 3) could be a result of a FcTe ligand oxidation and consequent dimerization
(Scheme 3) similar to the process described for (diphos)Pt(SAr)2 in [11].
Three next oxidation waves at 0.67, 0.84 and 0.97 V are quasi- reversible. In the
case of chelated complex there are two reversible one-electron oxidation waves of
ferrocenyl group at 0.48 and 0.59 V (Fig. 4). The nature of the third quasi-reversible
oxidation wave at 1.0 V in 2 is not clear yet and may involve the oxidation of Re or
Pt atoms.
Experimental Part
General Procedure
All reactions and manipulations were performed using standard Schlenk techniques
under an inert atmosphere of argon. Solvents were purified, dried and distilled under
an argon atmosphere prior to use. Re(CO)5Cl [12], (dppe)PtCl2 [13] and Fc2Te2 [14]
were prepared following the published procedures. NMR spectra were recorded at
Bruker Avance 300 and Bruker Avance 400 spectrometers.
Fig. 1 The solid state structure of 1 showing its non- hydrogen thermal ellipsoids at the 50 % probability
level. Hydrogen atoms are omitted for clarity. Selected intramolecular distances (A˚´
) P(2)–Pt(1) 2.255(1),
Pt1–P1 2.258(1), Pt1–Te1 2.6091(5), Pt1–Te2 2.6254(5), Te2–C1 1.109(6), Te1–C1 2.113(4), Te1–Fe1
3.6116(8), Te2–Fe2 3.578(1), Te2–C41 3.399(5), Te2–C42 3.687(6), Te2–C46 3.986(6), Te1–C11
3.364(6), C15–Te1 3.527(6), Te1–C12 4.182(7), and bond angles (°): P(2)–Pt(1)–P1 85.45(5),
Te(2)–Pt(1)–Te1 88.79(1), Cpplane–Te(1) 173.82 Cpplane–Te(2) 172.57
A. A. Pasynskii et al.
123
5. Fig. 2 The solid state structure of 2 showing its non-hydrogen thermal ellipsoids at the 50 % probability
level. Hydrogen atoms are omitted for clarity. Selected intramolecular distances (A˚´
) Pt(1)–P(2) 2.263(2),
Pt(1)–P(1) 2.266(2), Pt(1)–Te(4) 2.6578(5), Pt(1)–Te(3) 2.6389(7), Te(3)–Re(2) 2.7948(5), Re(2)–Te(4)
2.7899(6), Re(2)–Cl(1) 2.481(3), Te(4)–Fe(5) 3.593(1), Te(3)–Fe(1) 3.657(1), and bond angles (°):
P(2)–Pt(1)–P(1) 86.20(6), Te(4)–Pt(1)–Te(3) 82.35(2), Pt(1)–Te(4)–Re(2) 92.60(2), Re(2)–Te(3)–Pt(1)
92.89(2)
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
-2
0
2
4
6
8
10
E / V vs. Ag
I / µA
Fig. 3 Cyclic voltammogram for complex 1 (2.4 mM) in the potentials range from -0.2 to 1.13 V on the
glassy carbon (GC) electrode at t = 0.1 V s-1
in CH2Cl2 with 0.2 M Bu4NPF6 as the supporting
electrolyte. Start potential is -0.25 V
Redox Active Platinum–Bis(Telluroferrocenyl) Complex
123
6. Synthesis of (dppe)Pt(TeFc)2 (1)
Benzophenone 0.02 g (0.11 mmol) and the suspension of sodium (0.3 g, 13.04 mmol)
in 10 mL THF were added subsequently to the magnetically stirred red solution
Fc2Te2 (0.2 g, 0.32 mmol) at room temperature. After stirring for 2, 5 h reaction
mixture turned greenish-yellow and was filtrated to the solid (dppe)PtCl2 (0.21 g
(0.32 mmol) and stirring for additional 3 h. The solvent was eliminated from resulting
orange-red reaction mixture under reduced pressure and the orange oily residue was
washed with heptane (2 9 5 mL), extracted with THF (10 mL) and filtrated. THF
filtrate was diluted with heptane (4 mL), concentrated under reduced pressure to 1/3 of
initial volume and kept at -15 °C for 24 h to provide yellow precipitate. Yield 0.27 g
(70 %).
The crystals suitable for the single-crystal XRD analysis were grown from the
NMR sample of 1 in CDCl3 layered with hexane.
P
Ph2
Pt
Ph2
P Te
Te
Fc
Fc
Pt
Te
Fc
-1e-
Ph2
P
P
Ph2
Pt
Te
Fc
P
Ph2
Ph2
P
2
2+
Scheme 3 Suggested mechanism for one-electron oxidation of (dppe)Pt(FcTe)2
-0.5 0.0 0.5 1.0 1.5 2.0
-10
-5
0
5
10
15
20
I / µA
E / V vs. Ag
Fig. 4 Cyclic voltammogram for complex 2 (3.4 mM) in the potentials range from -0.25 to 1.7 V on the
glassy carbon (GC) electrode at t = 0.1 V s-1
in CH2Cl2 with 0.2 M Bu4NPF6 as the supporting
electrolyte. Start potential is -0.25 V
A. A. Pasynskii et al.
123
7. IR spectra (KBr, m, cm-1
,): 1103, 736, 692, 532. Anal. Calc. for 1(C46H42Fe2-
P2PtTe2): C 45.33, H 3.47 %; Found: C 44.52, H 3.76 %.
1
H NMR (300 MHz, CDCl3, d ppm): 1.87 (m, 4H, Ph4P2C2H4), 3.66 (m, 4H,
C5H4), 3.77 (m, 4H, C5H4), 3.95 (s, 10H C5H5), 7.05–7.78 (m, 20H, Ph4P2C2H4).
31
P NMR (121.5 MHz, CDCl3, d ppm): 44.94 (1
JPt–P = 2848 Hz, 2
JTe-P =
59 Hz).
125
Te NMR (94.7 MHz, CDCl3, d ppm): 65.2 (apparent triplet, 2
JTe-P = 59 Hz).
Synthesis of dppePt(l-TeFc)2Re(CO)3Cl (2)
Solid Re(CO)5Cl (0.042 g, 0.115 mmol) was stirred at 60 °C for 1 h in dry toluene
(10 mL) until almost complete dissolution and after addition of solid (dppe)Pt(FcTe)2
(0.14 g, 0.115 mmol) the reaction mixture was refluxed for 1 h. Then cooling to room
temperature gave an oily precipitate which solidified at pest ling with heptane (3 mL).
The solution with solidified orange residue was heated to the boiling temperature and
slowly cooled in an oil bath to room temperature resulting well-formed orange prisms
suitable for the single-crystal XRD analysis.
Yield 0.143 g (82 %). Sample for NMR and elemental analysis was recrystal-
lized from CH2Cl2/hexane mixture.
IR-spectrum (KBr, m, cm-1
): 2003, 1898, 1870, 1105, 821, 690, 531. Anal.Calc.
for 2 (C49H42ClFe2O3P2PtReTe2): C 38.61, H 2.78 %; Found: C 38.68, H 3.54 %.
1
H NMR (400 MHz, CDCl3, d ppm): 1.71–1.24 (br. m., 4H, Ph4P2C2H4), 2.89 (br.
s., 1H, C5H4), 3.27 (br. s., 1H, C5H4), 3.58 (br. s., 1H, C5H4), 3.77 (br. s., 1H, C5H4),
4.01 (br. s., 1H, C5H4), 4.11 (s, 5H, C5H5), 4.15 (s, 5H, C5H5), 4.21 (br. s., 1H, C5H4),
4.40 (br. s., 1H, C5H4), 4.67(br. s., 1H, C5H4), 7.30–7.81 (m, Ph4P2C2H4).
31
P NMR (162.0 MHz, CDCl3, d ppm): 37.8 (br. 1
JPt–P 2987 Hz), 41.0 (br. 1
JPt–P
2790 Hz).
Crystal Structure Determination of Compound 1 and 2
Relevant crystallographic data and details of measurements are given in Table 1.
A Bruker APEX II CCD area detector diffractometer equipped with a graphite-
monochromated Mo Ka radiation (0.71070 A˚ ) was used for the cell determination
and intensity data collection for compound 1 and 2. The structure was solved by
direct methods (SHELXS-97) and refined by full-matrix least squares against F2
using SHELXL-97 software [15]. Non-hydrogen atoms were refined with
anisotropic thermal parameters. All hydrogen atoms were geometrically fixed and
refined using a riding model.
Electrochemistry
The cyclic voltammograms (CV) of complexes 1 and 2 were recorded on a PAR 273
potentiostat/galvanostat (Princeton Applied Research) with the standard software.
The measurements were carried out in a thermostatically controlled three-electrode
electrochemical cell under a high purity argon atmosphere. A SU-2000 (0.0078 cm2
)
glassy carbon disk pressed in Teflon served as the working electrode and a platinum
Redox Active Platinum–Bis(Telluroferrocenyl) Complex
123
8. grid (1 cm2
) was used as the auxiliary electrode. The potentials were measured versus
the silver reference electrode in the same solution. The measurements were carried out
in dichloromethane with 0.2 M Bu4NPF6 as the supporting electrolyte. The potential
sweep rates were in the range from 0.050 to 1.0 V s-1
.
Table 1 Crystal data and structure refinement for compounds 1,2
Compound 1 2
Empirical formula C47H43Cl3Fe2P2PtTe2 C49H42ClFe2O3P2PtReTe2
Formula weight 1338.09 1524.41
Temperature, K 153(2) 150(2)
Wavelength (A˚´
) 0.71073
Crystal system Triclinic
Space group P-1
Unit cell dimensions
a (A˚´
) 11.5498(13) 11.7331(12)
b (A˚´
) 14.1088(15) 12.5142(13)
c (A˚´
) 14.6890(17) 18.701(2)
a (°) 100.885(2) 71.808(2)
b (°) 97.291(2) 81.442(2)
c (°) 92.558(2) 63.644(2)
Volume (A˚´ 3
) 2,325.8(4) 2,337.3(4)
Z 2 2
Density (calculated)
(mg/m3
)
1.911 2.166
Absorption coefficient (mm-1
) 5.118 7.563
F(000) 1,280 1,432
Theta range for data collection (°) 2.12–29.00. 2.07–27.50
Index ranges -15 B h B 15,
-19 B k B 19,
-20 B l B 19
-15 B h B 15,
-16 B k B 16,
-24 B l B 24
Reflections collected 25,446 20,847
Independent reflections 12,251 [R(int) = 0.0378] 10,598 [R(int) = 0.0259]
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.784 and 0.629 0.5829 and 0.3596
Refinement method Full-matrix least-squares on F2
Data/restraints/parameters 12,251/0/514 10,598/0/550
Goodness-of-fit on F2
1.009 0.831
Final R indices [I [ 2sigma(I)] R1 = 0.0413, wR2 = 0.1024 R1 = 0.0361, wR2 = 0.1050
R indices (all data) R1 = 0.0547, wR2 = 0.1105 R1 = 0.0488, wR2 = 0.1156
Largest diff. peak and hole, e (A˚´ -3
) 4.788 and -1.310 2.891 and -1.472
A. A. Pasynskii et al.
123
9. Acknowledgments We gratefully acknowledge the financial support from the Russian Foundation for
Basic Research (Grant 13-03-92691, 12-03-00860, 13-03-12415) and RF President Fellowship (MK
5635.2013.03).
Appendix A
Atomic coordinates and other structural parameters of 1–2 have been deposited with
the Cambridge Crystallographic Data Center (nos. CCDC 997651 (1), CCDC
997652 (2).
Supplementary data associated with this article can be found, in the online
version, at https://www.ccdc.cam.ac.uk/services/structure_deposit/.
References
1. T. S. A. Hor (1996). J. Cluster Sci. 3, 263.
2. T. Nakagawa, H. Seino, and Y. Mizobe (2010). J. Organomet. Chem. 695, 137.
3. A. A. Pasynskii, Yu. V. Torubaev, A. V. Pavlova, S. S. Shapovalov, I. V. Skabitsky, and G.
L. Denisov (2014). Russ. J. Coord. Chem. 40(09), P000. doi:10.7868/S0132344X14090060.
4. I. V. Skabitsky, Yu V Torubaev, Zh V Dobrokhotova, and E. V. Krasil’nikova (2005). Russ. J. Inorg.
Chem. 50, 1197.
5. M. Risto, E. M. Jahr, M. S. Hannu-Kuure, R. Oilunkaniemi, and R. S. Laitinen (2007). J. Organomet.
Chem. 692, 2193.
6. A. A. Pasynskii, I. V. Skabitsky, and Yu V Torubaev (2005). Russ. Chem. Bull. 54, 1552.
7. Y. Torubaev, P. Mathur, M. Tauqeer, M. M. Shaikh, G. K. Lahiri, A. Pasynskii, A. Pavlova, and V.
Grinberg (2014). J. Organomet. Chem. 749, 115.
8. N. V. Kirij, W. Tyrra, I. Pantenburg, D. Naumann, H. Scherer, D. Naumann, and Yu L Yagupolskii
(2006). J. Organomet. Chem. 691, 2679.
9. B. Cordero, V. Gromez, A. E. Platero-Prats, M.Revres, J.Echeverrrıa, E. Cremades, F. Barragran and
S. Alvarez (2008) Dalton. Trans. 2832.
10. A. Pasynskii (2011). Russ. J. Coord. Chem. 37, 801.
11. S.-K. Lee, O. Jeannin, M. Fourmigue, W. Suh, and D.-Y. Noh (2012). J. Organomet. Chem. 716, 237.
12. E.W. Abel and G. Wilkinson (1959). J. Chem. Soc. 1501.
13. D. A. Slack and M. C. Baird (1977). Inorg. Chim. Acta. 24, 277.
14. Y. Nishibayashi, T. Chiba, J. D. Singh, S. Uemura, and S. Fukuzawa (1994). J. Organomet. Chem.
473, 205.
15. G. M. Sheldrick (2008). Acta. Crystallogr. A64, 112.
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123