This document reports on the synthesis and characterization of ferrocenyltelluride derivatives. It describes the reaction of ferrocenyltelluride iodide ([FcTeI]) with iron pentacarbonyl to form either a monomeric complex bearing a diferrocenylditelluride ligand or a dimeric complex with a bridging ferrocenyltelluride ligand. It also discusses the synthesis and properties of complexes featuring terminal ferrocenyltelluride ligands, including their electrochemical behavior and ability to undergo halogenation. Additionally, it examines the use of one such complex as a metalloligand to form a three-iron containing framework.
Carbon belongs to the group IV of the periodic table.
It has four electrons in its outermost orbit, so its valency is four.
Carbon is a non-metal.
Why so many Carbon Compounds in nature
Because carbon is chemically unique.
Only carbon atoms have the ability to combine with themselves to form long chains
The number of carbon compounds is larger than that of all other elements put together.
Occurrence of carbon
The name ‘carbon’ is derived from the Latin
word ‘carbo’ meaning coal. Carbon is found in
nature in free as well as compound state. Carbon in
the free state is found as diamond and graphite, and
in the combined state in the following compounds.
1. As carbon dioxide and in the form of carbonates
such as calcium carbonate, marble, calamine
(ZnCO3)
2. Fossil fuel – coal, petroleum, natural gas
3. Carbonaceous nutrients – carbohydrates,
proteins, fats
4. Natural fibres – cotton, wool, silk
Properties of carbon
Allotropic nature of Carbon
Allotropy - Some elements occur in nature in more than one form. The chemical properties
of these different forms are the same but their physical properties are different. This
property of elements is called allotropy. Like carbon, sulphur and phosphorus also exhibit
allotropy.
Allotropes of carbon
A. Crystalline forms
1. A crystalline form has a regular and definite arrangement of atoms.
2. They have high melting points and boiling points.
3. A crystalline form has a definite geometrical shape, sharp edges and plane surfaces.
Carbon belongs to the group IV of the periodic table.
It has four electrons in its outermost orbit, so its valency is four.
Carbon is a non-metal.
Why so many Carbon Compounds in nature
Because carbon is chemically unique.
Only carbon atoms have the ability to combine with themselves to form long chains
The number of carbon compounds is larger than that of all other elements put together.
Occurrence of carbon
The name ‘carbon’ is derived from the Latin
word ‘carbo’ meaning coal. Carbon is found in
nature in free as well as compound state. Carbon in
the free state is found as diamond and graphite, and
in the combined state in the following compounds.
1. As carbon dioxide and in the form of carbonates
such as calcium carbonate, marble, calamine
(ZnCO3)
2. Fossil fuel – coal, petroleum, natural gas
3. Carbonaceous nutrients – carbohydrates,
proteins, fats
4. Natural fibres – cotton, wool, silk
Properties of carbon
Allotropic nature of Carbon
Allotropy - Some elements occur in nature in more than one form. The chemical properties
of these different forms are the same but their physical properties are different. This
property of elements is called allotropy. Like carbon, sulphur and phosphorus also exhibit
allotropy.
Allotropes of carbon
A. Crystalline forms
1. A crystalline form has a regular and definite arrangement of atoms.
2. They have high melting points and boiling points.
3. A crystalline form has a definite geometrical shape, sharp edges and plane surfaces.
Selective Oxidation of Cyclohexene, Toluene and Ethyl Benzene Catalyzed by Bi...Iranian Chemical Society
Bis-(L-tyrosinato)copper(II) was reacted with 3-(chloropropyl)-trimethoxysilane functionalized silica that has infused magnetite to yield a magnetically separable catalyst in which the copper carboxylate is covalently linked to the silica matrix through the silane linkage. The immobilized catalyst has been characterized by spectroscopic studies (such as FT-IR, EPR, Magnetic Measurement, SEM) and chemical analyses. The immobilized catalytic system functions as an efficient heterogeneous catalyst for oxidation of cyclohexene, toluene and ethyl benzene in the presence of hydrogen peroxide (as an oxidant) and sodium bicarbonate (a co-catalyst). The reaction conditions have been optimized for solvent, temperature and amount of oxidant and catalyst. Comparison of the encapsulated catalyst with the corresponding homogeneous catalyst showed that the heterogeneous catalyst had higher activity and selectivity than the homogeneous catalyst. The immobilized catalyst could be readily recovered from the reaction mixture by using a simple magnet, and reused up to five times without any loss of activity.
A complete summary of the chapter carbon and its compounds. Every topic has been discussed effectively and provided with pictures for further reference.
A detailed study of Transition Metal Complexes of a Schiff base with its Phys...Abhishek Ghara
The many activities of metal ions in biology have stimulated the development of metal based therapeutics. It has been found that biologically active compounds become more effective and bacteriostatic upon chelation with metal ions also the biological activity of many drugs has been shown to be enhanced on complexing with metal ions, hence promoting their use in Pharmacology. The present work deals with the synthesis of metal complexes derived from a novel Schiff base drug synthesized from urea and salicylaldehyde and its physico-chemical analysis to find out ligand- metal ratio of this complex in solution. For the structure elucidation of these complexes “Monovariation method (Mole ratio method/ Yoe-Jones Method)” has been used to ascertain the ligand-metal ratio in the complex. The stability constant of the formed complex was calculated by molar conductance measurement using Modified Job’s method (Method of Continuous Variations). The analysis has been carried out using conductometry. To confirm metal-ligand ratio, conductometric titrations were carried out at room temperature using analytical grade metal salts. Titrations were carried out with “systronics conductivity-meter” using dip type conductivity cell having cell constant 1 at room temperature.
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.
Synthesis and characterization of mixed ligand complexes of some metals with ...Taghreed Al-Noor
This paper presents the synthesis and study of some new mixed-liagnd complexes containing nicotinamide(C6H7N2O) symbolized (NA) and phenylalanine (C9H11NO2)symbolized (pheH)] with some metal ions.
The resulting products were found to be solid crystalline complexes which have been characterized by :Melting points, Solubility, Molar conductivity.
determination the percentage of the metal in the complexes by flame(AAS), magnetic susceptipibility, Spectroscopic Method [FT-IR and UV-Vis].
The proposed structure of the complexes using program , chem office 3D(2006) .
The general formula have been given for the prepared complexes :[M(NA)2(phe)]cl
M(II): Mn(II) ,Co(II) , Ni(II) , Cu(II) , Zn(II) , Cd(II) & Hg(II) .
NA = Nicotinamide= C6H7N2O
Phe - = phenylalanine ion = C9H10NO2
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
Synthesis, Characterization and antimicrobial activity of some novel sulfacet...iosrjce
IOSR Journal of Applied Chemistry (IOSR-JAC) is a double blind peer reviewed International Journal that provides rapid publication (within a month) of articles in all areas of applied chemistry and its applications. The journal welcomes publications of high quality papers on theoretical developments and practical applications in Chemical Science. Original research papers, state-of-the-art reviews, and high quality technical notes are invited for publications.
CHE3063 Organometallic Chemistry, Molecular Symmetry and InorgJinElias52
CHE3063 Organometallic Chemistry, Molecular Symmetry and Inorganic Electronics
Coursework Questions 2021-22
Deadline: 7th December 2021 submit to SurreyLearn assignments folder
Note that some of these questions are formative (F), meaning that you may complete them and ask
for quick feedback from Dr Turner or Dr Riddlestone. The summative (S) questions will be used to
determine your mark for this coursework.
The following abbreviations are used
Cy = cyclohexyl, Et = ethyl, Ph = phenyl, Me = methyl, bipy = 2,2'-bipyridine, Cp = cyclopentadienyl
Formative Questions
F1. Determine the metal valence electron count for each of the following compounds.
(i) [(5-Cp)Rh(2-C2H4)(PMe3)]
(ii) [TiCl2(5- Cp)]
(iii) [(3-C3H5)2Rh(2-Cl)2Rh(3-C3H5)2]
(iv) [Rh(Cl)(H)2(2-C2H4)(PPh3)2]
(v) [Ir(H2)2(H)2(PCy3)]+
(vi) [(5- Cp)Co(Me)(PMe3)2]+
[Formative, Dr Turner]
F2. Using symmetry arguments, show if and how vibrational spectroscopy can be used to
distinguish between pure geometric isomers of [Cr(PMe3)4(CO)2]. Would you be able to
recognise a mixture of isomers from vibrational spectroscopy?
[Formative, Dr Turner]
F3. The hydroformylation of 1-butene can be catalysed by [RhH(CO)(PPh3)3] and results in the
formation of major and minor products. Draw the structures of both products and construct
a catalytic cycle for the formation of the major product. Why are both linear and branched
products both formed in this reaction?
[Formative, Dr Riddlestone]
Summative Questions
S1. At 30°C the 1H-NMR spectrum of [Fe(CO)2(Cp)2] shows two peaks, one of which is at 5.6
ppm. At -55°C the spectrum shows 3 peaks at 4, 5.6 and 6.5 ppm with relative intensity
4:5:1, respectively. Further cooling results in the broad peak at 4 ppm splitting into two
equally intense multiplets. Fully explain this data and sketch the structure of the compound.
[6]
S2. Explain all the factors that could affect the carbonyl stretching frequency in the generalized
compound [MwLx(CO)y]z. M is a metal atom or ion; L represents non-carbonyl ligands; y is at
least 1, w and x are positive integers, z is a positive or negative integer.
[8]
S3. The following table lists the vibrational bands for an isomer of N2F2.
Band position (cm-1)
infra-red spectrum
Band position (cm-1)
Raman spectrum
360 592
421 1010
989 1636
(i) Show how a simple calculation can determine the total number of vibrational bands.
Fully explain the origin of the method that you use.
[3]
(ii) Which isomer of N2F2 is characterized by the data above? Explain a method to
determine your answer without having to do any calculations.
[3]
(iii) For the isomer, chosen in part (ii), determine the irreducible representations for the
normal vibrational modes. Determine which of the irreducible representations are
observable in Raman and IR spectroscopies. Explain your reasoning.
[9]
(iv) One of the vibrations, listed in the table, is the s ...
Photo-induced reduction of CO2 using a magnetically separable Ru-CoPc@TiO2@Si...Pawan Kumar
An efficient photo-induced reduction of CO2 using magnetically separable Ru-CoPc@TiO2@SiO2@Fe3O4
as a heterogeneous catalyst in which CoPc and Ru(bpy)2phene complexes were attached to a solid
support via covalent attachment under visible light is described. The as-synthesized catalyst was characterized
by a series of techniques including FTIR, UV-Vis, XRD, SEM, TEM, etc. and subsequently tested for
the photocatalytic reduction of carbon dioxide using triethylamine as a sacrificial donor and water as a
reaction medium. The developed photocatalyst exhibited a significantly higher catalytic activity to give a
methanol yield of 2570.78 μmol per g cat after 48 h.
Selective Oxidation of Cyclohexene, Toluene and Ethyl Benzene Catalyzed by Bi...Iranian Chemical Society
Bis-(L-tyrosinato)copper(II) was reacted with 3-(chloropropyl)-trimethoxysilane functionalized silica that has infused magnetite to yield a magnetically separable catalyst in which the copper carboxylate is covalently linked to the silica matrix through the silane linkage. The immobilized catalyst has been characterized by spectroscopic studies (such as FT-IR, EPR, Magnetic Measurement, SEM) and chemical analyses. The immobilized catalytic system functions as an efficient heterogeneous catalyst for oxidation of cyclohexene, toluene and ethyl benzene in the presence of hydrogen peroxide (as an oxidant) and sodium bicarbonate (a co-catalyst). The reaction conditions have been optimized for solvent, temperature and amount of oxidant and catalyst. Comparison of the encapsulated catalyst with the corresponding homogeneous catalyst showed that the heterogeneous catalyst had higher activity and selectivity than the homogeneous catalyst. The immobilized catalyst could be readily recovered from the reaction mixture by using a simple magnet, and reused up to five times without any loss of activity.
A complete summary of the chapter carbon and its compounds. Every topic has been discussed effectively and provided with pictures for further reference.
A detailed study of Transition Metal Complexes of a Schiff base with its Phys...Abhishek Ghara
The many activities of metal ions in biology have stimulated the development of metal based therapeutics. It has been found that biologically active compounds become more effective and bacteriostatic upon chelation with metal ions also the biological activity of many drugs has been shown to be enhanced on complexing with metal ions, hence promoting their use in Pharmacology. The present work deals with the synthesis of metal complexes derived from a novel Schiff base drug synthesized from urea and salicylaldehyde and its physico-chemical analysis to find out ligand- metal ratio of this complex in solution. For the structure elucidation of these complexes “Monovariation method (Mole ratio method/ Yoe-Jones Method)” has been used to ascertain the ligand-metal ratio in the complex. The stability constant of the formed complex was calculated by molar conductance measurement using Modified Job’s method (Method of Continuous Variations). The analysis has been carried out using conductometry. To confirm metal-ligand ratio, conductometric titrations were carried out at room temperature using analytical grade metal salts. Titrations were carried out with “systronics conductivity-meter” using dip type conductivity cell having cell constant 1 at room temperature.
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.
Synthesis and characterization of mixed ligand complexes of some metals with ...Taghreed Al-Noor
This paper presents the synthesis and study of some new mixed-liagnd complexes containing nicotinamide(C6H7N2O) symbolized (NA) and phenylalanine (C9H11NO2)symbolized (pheH)] with some metal ions.
The resulting products were found to be solid crystalline complexes which have been characterized by :Melting points, Solubility, Molar conductivity.
determination the percentage of the metal in the complexes by flame(AAS), magnetic susceptipibility, Spectroscopic Method [FT-IR and UV-Vis].
The proposed structure of the complexes using program , chem office 3D(2006) .
The general formula have been given for the prepared complexes :[M(NA)2(phe)]cl
M(II): Mn(II) ,Co(II) , Ni(II) , Cu(II) , Zn(II) , Cd(II) & Hg(II) .
NA = Nicotinamide= C6H7N2O
Phe - = phenylalanine ion = C9H10NO2
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
Synthesis, Characterization and antimicrobial activity of some novel sulfacet...iosrjce
IOSR Journal of Applied Chemistry (IOSR-JAC) is a double blind peer reviewed International Journal that provides rapid publication (within a month) of articles in all areas of applied chemistry and its applications. The journal welcomes publications of high quality papers on theoretical developments and practical applications in Chemical Science. Original research papers, state-of-the-art reviews, and high quality technical notes are invited for publications.
CHE3063 Organometallic Chemistry, Molecular Symmetry and InorgJinElias52
CHE3063 Organometallic Chemistry, Molecular Symmetry and Inorganic Electronics
Coursework Questions 2021-22
Deadline: 7th December 2021 submit to SurreyLearn assignments folder
Note that some of these questions are formative (F), meaning that you may complete them and ask
for quick feedback from Dr Turner or Dr Riddlestone. The summative (S) questions will be used to
determine your mark for this coursework.
The following abbreviations are used
Cy = cyclohexyl, Et = ethyl, Ph = phenyl, Me = methyl, bipy = 2,2'-bipyridine, Cp = cyclopentadienyl
Formative Questions
F1. Determine the metal valence electron count for each of the following compounds.
(i) [(5-Cp)Rh(2-C2H4)(PMe3)]
(ii) [TiCl2(5- Cp)]
(iii) [(3-C3H5)2Rh(2-Cl)2Rh(3-C3H5)2]
(iv) [Rh(Cl)(H)2(2-C2H4)(PPh3)2]
(v) [Ir(H2)2(H)2(PCy3)]+
(vi) [(5- Cp)Co(Me)(PMe3)2]+
[Formative, Dr Turner]
F2. Using symmetry arguments, show if and how vibrational spectroscopy can be used to
distinguish between pure geometric isomers of [Cr(PMe3)4(CO)2]. Would you be able to
recognise a mixture of isomers from vibrational spectroscopy?
[Formative, Dr Turner]
F3. The hydroformylation of 1-butene can be catalysed by [RhH(CO)(PPh3)3] and results in the
formation of major and minor products. Draw the structures of both products and construct
a catalytic cycle for the formation of the major product. Why are both linear and branched
products both formed in this reaction?
[Formative, Dr Riddlestone]
Summative Questions
S1. At 30°C the 1H-NMR spectrum of [Fe(CO)2(Cp)2] shows two peaks, one of which is at 5.6
ppm. At -55°C the spectrum shows 3 peaks at 4, 5.6 and 6.5 ppm with relative intensity
4:5:1, respectively. Further cooling results in the broad peak at 4 ppm splitting into two
equally intense multiplets. Fully explain this data and sketch the structure of the compound.
[6]
S2. Explain all the factors that could affect the carbonyl stretching frequency in the generalized
compound [MwLx(CO)y]z. M is a metal atom or ion; L represents non-carbonyl ligands; y is at
least 1, w and x are positive integers, z is a positive or negative integer.
[8]
S3. The following table lists the vibrational bands for an isomer of N2F2.
Band position (cm-1)
infra-red spectrum
Band position (cm-1)
Raman spectrum
360 592
421 1010
989 1636
(i) Show how a simple calculation can determine the total number of vibrational bands.
Fully explain the origin of the method that you use.
[3]
(ii) Which isomer of N2F2 is characterized by the data above? Explain a method to
determine your answer without having to do any calculations.
[3]
(iii) For the isomer, chosen in part (ii), determine the irreducible representations for the
normal vibrational modes. Determine which of the irreducible representations are
observable in Raman and IR spectroscopies. Explain your reasoning.
[9]
(iv) One of the vibrations, listed in the table, is the s ...
Photo-induced reduction of CO2 using a magnetically separable Ru-CoPc@TiO2@Si...Pawan Kumar
An efficient photo-induced reduction of CO2 using magnetically separable Ru-CoPc@TiO2@SiO2@Fe3O4
as a heterogeneous catalyst in which CoPc and Ru(bpy)2phene complexes were attached to a solid
support via covalent attachment under visible light is described. The as-synthesized catalyst was characterized
by a series of techniques including FTIR, UV-Vis, XRD, SEM, TEM, etc. and subsequently tested for
the photocatalytic reduction of carbon dioxide using triethylamine as a sacrificial donor and water as a
reaction medium. The developed photocatalyst exhibited a significantly higher catalytic activity to give a
methanol yield of 2570.78 μmol per g cat after 48 h.
Bis-perfluorocycloalkenyl (PFCA) aryl ether monomers towards a versatile clas...aaaa zzzz
A unique class of perfluorocycloalkenyl (PFCA) aryl ether monomers was synthesized from commercially available perfluorocycloalkenes (PFCAs) and bisphenols in good yields. This facile one pot reaction of per- fluorocycloalkenes, namely, octafluorocyclopentene (OFCP), and decafluorocyclohexene (DFCH), with bisphenols occurs at room temperature via an addition–elimination reaction in the presence of a base. The synthesis of PFCA monomers and their condensation with bisphenols lead to perfluorocycloalkenyl (PFCA) aryl ether homopolymers and copolymers with random and/or alternating polymer architectures.
Published by Elsevier Ltd.
Photo-induced reduction of CO2 using a magnetically separable Ru-CoPc@TiO2@Si...Pawan Kumar
An efficient photo-induced reduction of CO2 using magnetically separable Ru-CoPc@TiO2@SiO2@Fe3O4
as a heterogeneous catalyst in which CoPc and Ru(bpy)2phene complexes were attached to a solid
support via covalent attachment under visible light is described. The as-synthesized catalyst was characterized
by a series of techniques including FTIR, UV-Vis, XRD, SEM, TEM, etc. and subsequently tested for
the photocatalytic reduction of carbon dioxide using triethylamine as a sacrificial donor and water as a
reaction medium. The developed photocatalyst exhibited a significantly higher catalytic activity to give a
methanol yield of 2570.78 μmol per g cat after 48 h.
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 .
I -s2o.100 Chapter 3 Chemical BondsUWL tnteractive ve.docxadampcarr67227
I -s'2o.
100 Chapter 3 Chemical Bonds
UWL tnteractive versions of these problems may be assigned
in OWL.
Orange-numbered problems are applied.
Section 3.2 What ls the Octet Rule?
3.17 Answer true or false. '
(a) The octet rule refers to the chemical bonding
patterns of the first eight elements of the
Periodic Table.
(b) The octet rule refers to the tendency ofcertain
elements to react in such a way that they achieve
an outer shell ofeight valence electrons.
(c) In gaining electrons, an atom becomes a posi-
tively charged ion called a cation.
(d) When an atom forms an ion, only the number of
. valence electrons changes; the number ofprotons
and neutrons in the nucleus does not change.
(e) In forming ions, Group 2A elements typically
lose two electrons to become cations with a
charge of +2.
(f) In forming an ion, a sodium atom (1s22s22p63s1)
completes its valence shell by adding one elec-
tron to filI its 3s shell (k22s22p63s2).
(g) The elements of Group 6A typically react by ac-
cepting two electrons to become anions with a
charge of -2.
(h) With the exception of hydrogen, the octet rule
applies to all elements in periods 1,2, and 3.
(i) Atoms and the ions derived from them have very
similar physical and chemical properties.
3.18 How many electrons must each atom gain or lose
to acquire an electron configuration identical to the
noble gas nearest to it in atomic number?
(a) Li (b) Cl (c) P (d) Al
(e) Sr (f) S (e) Si (h) O
3.19 Show how each chemical change obeys the octet
rule.
(a) Lithium forms Li* (b) Oxygen forms O
Show how each chemical change obeys the octet rule.
(a) Hydrogen forms H- (hydride ion)
(b) Aluminum forms Al3+
3,2L Write the formula for the most stable ion formed by
each element.
(a) Mg (b) F (c)
(d) s (e) K (I)
3.22 Why is Li- not a stable ion?
3.23 Predict which ions are stable:
(a) I- (b) Se2+ (c) Na* (d) 52- (e) tr12+ (fl Ba8+
3,24 Predict which ions are stable:
(a) Br2- (b) C4- (c) Ca*
(d) Ar* (e) Na* (I) Cs*
a
3.25 Why are carbon and silicon reluctant to foil
bonds?
3.26 Table 3.2 shows the following ions of co14m
and Cu2*. Do these violate the octet rule?
Section 3.3 How Do We Name Anions
and Cations?
5.27 Answer true or false.
(a) For Group 1A and Group 2A elements,fte
of the ion each forms is simply the nare
element followed by the word ion; for
Mg2* is named magnesium ion.
(b) H+ is named hydronium ion, and H is
hydride ion.
(c) The nucleus of H* consists of one proton
neutron.
(d) Many transition and inner transition
form more than one positively charged irn I
(e) In naming metal cations with two diffemed
charges, the suffix -oas refers to the ion
a charge of + 1 and -ic refers to the ion wift
charge of +2.
(f) Fe3* may be named either iron(III) ion or
(g) The anion derived from a bromine atom is
bromine ion.
(h) The anion derived from an oxygen atomis
named oxide ion.
(i) HCO; is named hydrogen carbonate ion- .
0) The prefrx bi- in the name "bicarbonate'im
indicates that this ion h.
Bis-perfluorocycloalkenyl (PFCA) aryl ether monomers towards a versatile clas...Babloo Sharma, Ph.D.
A unique class of perfluorocycloalkenyl (PFCA) aryl ether monomers was synthesized from commercially available perfluorocycloalkenes (PFCAs) and bisphenols in good yields. This facile one pot reaction of perfluorocycloalkenes, namely, octafluorocyclopentene (OFCP), and decafluorocyclohexene (DFCH), with bisphenols occurs at room temperature via an addition–elimination reaction in the presence of a base. The synthesis of PFCA monomers and their condensation with bisphenols lead to perfluorocycloalkenyl (PFCA) aryl ether homopolymers and copolymers with random and/or alternating polymer architectures.
In this unit following contents are covered:
• Introduction
• Classification of Organometallic Compounds
• Nomenclature of Organometallic Compounds
• Modern Classification of Organometallic Compounds
• Metal Carbonyls
• Classification of Metal Carbonyls
1. Nickel Carbonyl
2. Iron Carbonyl
3. Chromium Carbonyls
• EAN
• Structure of Metal Carbonyls on the basis of VBT
This is very useful for UG students.
2. additional iron atoms into a molecule of the precursor. Secondly,
the electron-donating ferrocenyl fragment increases the nucleo-
philicity of the associated tellurium atom. Finally, the ferrocenyl
group can be easily oxidized electrochemically or by oxidative
agents. Our recent investigation of diferrocenyleditelluride com-
plexes of VI group carbonyls demonstrated general similarity with
their phenyl congeners, particularly the electron-compensating
cleavage of the TeeTe bond during the photochemical decarbon-
ylation (Scheme 2) [3] (Fig. 1).
It was also interesting to compare the reactivity of [FcTeI] to-
wards Fe(CO)5 with that of its phenyl congener [PhTeI] [4] and
investigate the decarbonylation of CpFe(CO)2TeFc and of its use as a
possible metalloligand.
Results and discussion
Depending on the ratio of the starting reagents an interaction
between FcTeeTeI2Fc and Fe(CO)5 gives the monomeric complex
(Fc2Te2)Fe(CO)3I2 (1) or the dimeric complex [(CO)3IFe(m-TeFc)]2 (2)
if an excess of Fe(CO)5 was used (Scheme 3):
In complex 1 the molecule of diferrocenylditelluride is coordi-
nated only by one tellurium atom completing the octahedral co-
ordination surrounding of the iron atom. The ironetellurium
distance is shortened (Te1eFe1 2.580(1) Å) as compared to the CRS
(2.70 Å) [5], similarly to the rest of known transition metal
organotellurides. This shortening is usually rationalized in terms of
additional back donation М / Te [6] and is accompanied by the
consequent elongation of the TeeTe distance (2.770(1) Å as
compared to 2.704e2.721 Å in a “free” Fc2Te2 [7,8]. It is interesting
that in 1 the “dropping” of Te(2) atom from the cyclopentadienyl
plane to the iron atom of the ferrocenyl fragment takes place
(a ¼ 11.8). In the dimeric complex 2 (Fig. 2), iodide and bridging
telluroferrocenyl ligands were found at the same (as in 1) distances
from the iron centers. The same similarity we have noticed in the
pair of their phenyl congeners: (CO)3FeI2(Ph2Те2) and [(CO)3IFe-
TePh]2 [9].
Complex CpFe(CO)2TeFc 3 (Fig. 3) containing the terminal fer-
rocenyltelluride ligand instead of the iodine atom was obtained as a
brown crystalline product of the thermal interaction between
[Ср(CO)2Fe]2 and Fc2Te2, by analogy with the preparation of
CpFe(CO)2TePh [10].
In 3 the FeeТе distance (2.589(3) Å) is significantly longer as
compared to that in CpFe(CO)2TePh (FeeTe 2.528 Å), since the
additional Fe / Te back donation is reduced because an electron
withdrawing phenyl is substituted for electron donating ferrocenyl
group.
The cyclic voltammogram (CV) for complex 3 (Fig. 4, curve 1)
demonstrates a quasi-reversible one-electron oxidation wave at
0.24 V apparently, arising from the ferrocenyl fragment oxidation,
and the quasi-reversible two-electron oxidation wave at 0.76 V,
Scheme 1. Formation and thermolyses of Ph2Te2 complexes of Mo-carbonyls.
Scheme 2. Formation and transformation of Fc2Te2 e complexes of Cr-, Mo- and W-carbonyls.
Y.V. Torubaev et al. / Journal of Organometallic Chemistry 777 (2015) 88e95 89
3. arising from the oxidation of the tellurium and the second iron
atoms.
Being treated with the elemental bromine or iodine, complex 3
easily attaches two halogen atoms at the tellurium center so that
the FeeTe bond remains untouched (Scheme 4). The structures of
Fig. 1. The solid state structure of 1 in the thermal ellipsoids at the 50% probability
level. Due to the disorder carbon atoms of Cp-rings where refined in isotropic model
and are shown as spheres. Hydrogen atoms are omitted for clarity. Selected intra-
molecular distances (Å):Te1eTe2 2.770(1), Te1eFe1 2.580(1), Fe1eI1 2.660(2), Fe1eI2
2.648(2); and angles (): CpeTe2 168.20, CpeTe1 176.78.
Fig. 2. The solid state structure of 2 in thermal ellipsoids at the 50% probability level.
Because of the disorder carbon atoms of Cp-rings are shown as spheres. Hydrogen
atoms are omitted for clarity. Selected intramolecular distances (Å): Fe1eTe 2.5965(5),
FeeI 2.6452(6).
Fig. 3. The solid state structure of 3 in thermal ellipsoids at the 50% probability level.
Due to the disorder carbon atoms of Cp-ring at Fe1 where refined in isotropic model
and are shown as spheres. Hydrogen atoms are omitted for clarity. Selected intra-
molecular distances (Å): Fe1eTe1 2.591(2).
Scheme 3. Formation of 1 and 2.
Fig. 4. The cyclic voltammogram (CV) for complex 3 (curve 1) and for complex 5
(curve 2).
Scheme 4. Formation of 3e5.
Y.V. Torubaev et al. / Journal of Organometallic Chemistry 777 (2015) 88e9590
4. corresponding dihalides CpFe(CO)2TeХ2Fc, Х ¼ Br and I (4 and 5
respectively) were determined by XRD method (Figs. 5 and 6):
The CV diagram for the complex 5 (Fig. 4, curve 2) contains a
quasi-reversible one-electron oxidation wave at 0.75 V, arising
from the ferrocenyl fragment oxidation, and a quasi-reversible one-
electron oxidation wave at 0.98 V, arising from the oxidation of the
second iron atom in the CpFe(CO)2 moiety.
Similarly to its phenyl congener, CpFe(CO)2TePh, complex 3 can
be used as a metal-containing building block in a design of the
complex metal-chalcogene frameworks. For example, 3 can coor-
dinate a Fe(CO)3I2 fragment to give CpFe(CO)2(m-TeFc)Fe(CO)3I2 (7)
which incorporates three iron atoms in different coordination
surrounding (Scheme 5, Fig. 7).
In complexes 4, 5, 6 the Fe1eТе1 distances (2.522(2), 2.5328(6),
2.5574(11) Å) are significantly shorter as compared to the starting
complex 3 (FeeTe 2.591(2) Å). This effect can be rationalized in
terms of the electron density withdrawal from Te atom and
consequent increase of the Fe / Te back donation from CpFe(CO)2
moiety. It is supported by Mossbauer data for complex 6.
In order to more completely characterize the properties of
compound 6 a M€ossbauer effect (ME) study was undertaken over
the temperature range 96 T 300 K. A representative spectrum
is shown in Fig. 8 from which it is evident that the three iron sites
are clearly resolved from each other. For the purposes of the
present discussion and in consonance with the numbering scheme
in Fig. 7, the Fe atom ligated to the Cp and two CO groups is
referred to as Fe1, the Fe atom of the ferrocene fragment is
referred to as Fe2, and the Fe atom ligated to two I and three CO
groups is referred to as Fe3. Fe1 and Fe3 atoms are directly bonded
to the central Te atom. Each of these three Fe resonances has a
well resolved isomer shift (IS) and quadrupole splitting (QS) as
will be discussed below.
The IS and QS parameters at 90 K are summarized in Table 1
from which it is seen that Fe1 and Fe3 have similar IS values,
while that of Fe2 (0.494 ± 0.012 mm sÀ1
) is close to that reported
for the parent ferrocene (0.537 ± 0.001 mm sÀ1
) as expected.
The temperature-dependence of the IS for Fe2 is well fitted by a
linear regression (R ¼ 0.98 for 11 data points) which, in turn leads
[11] to a value of Meff ¼ 127 ± 4 Da. The difference between this
value and the “bare” Fe mass is a measure of the covalency of the
Fe-to-ligand bonding. On the other hand the QS parameter is only
slightly sensitive to T and has a mean value of 2.425 ± 0.008 mm sÀ1
again similar to that of ferrocene at 90 K.
The temperature dependence of the logarithm of the area under
the resonance curve, which scales with the temperature-
dependence of the recoil-free fraction (f) is again well fitted by a
linear regression (R ¼ 0.997 for 10 data points) and will be dis-
cussed in more detail, below.
Fig. 5. The solid state structure of 4 in thermal ellipsoids at the 50% probability
level. Hydrogen atoms are omitted for clarity. Selected intramolecular distances
(Å): Fe1eTe1 2.522(2), Te1eBr2 2.712(2), Te1eBr1 2.768(2) Å, Fe2eTe1 3.713(3) Å.
Fig. 6. The solid state structure of 5 in thermal ellipsoids at the 50% probability
level. Hydrogen atoms are omitted for clarity. Selected intramolecular distances
(Å): Fe1eTe1 2.5328(6), Te1eI2 2.9855(4), Te1eI1 2.9420(4), Te1eFe2 3.6911(9) Å.
Scheme 5. Formation of 6.
Fig. 7. The solid state structure of 6 showing its associates in thermal ellipsoids at the
50% probability level. Hydrogen atoms are omitted for clarity. Selected intramolecular
distances (Å): Fe1eTe1 2.5574(11), Fe3eTe1 2.6381(11), Fe3eI3 2.5978(16), Fe3eI2
2.6533(11), Fe3eI1 2.677(2), Te1eC11 2.120(7) Å.
Y.V. Torubaev et al. / Journal of Organometallic Chemistry 777 (2015) 88e95 91
5. The IS and QS parameters for Fe1 and Fe3 are quite similar, as
noted from table and the temperature dependence of QS is essen-
tially temperature insensitive over the accessible range. There is,
however, a significant difference in d IS/dT for these two atoms
(5.95 ± 0.94 and 3.44 ± 0.88 Â 10À4
mm sÀ1
KÀ1
) respectively,
leading to Meff values of 67 ± 7 and 121 ± 25 Da for the two sites
with the latter presumably reflecting the influence of the two
massive iodine atom in the structure.
As has been pointed out earlier [12], the temperature depen-
dence of the recoil-free fraction can be related to the root-mean-
square-amplitude-of-vibration of the metal atom and compared
to the corresponding value extracted from the Ui,j parameters of the
single-crystal X-ray determination of 6. The temperature-
dependence of ln[A(T)/A(90)] for Fe2 is summarized graphically in
Fig. 9 and has a slope of (6.20 þ 0.060) Â 10À3
KÀ1
with a corre-
lation coefficient of 0.996 for 11 data points. The line has an
intercept (at T ¼ 0 K) of 0.595.
These data can be converted to the Ғ parameter (¼exp
k2
xave
2
) by adding 0.959 and extrapolation to T ¼ 0 K, making the
assumption that the zero-point contribution to the vibrational
amplitude in the ME temperature regime is negligible. The result-
ing Ғ values are summarized graphically in Fig. 10.
As noted above, the Ғ parameter can also be calculated from the
X-ray data, as shown in Fig. 10 and as noted, the agreement is quite
satisfactory. A similar sequence of data reductions has been ob-
tained for Fe1 and Fe3 of compound 6 and in general there is good
agreement between the Ғ values calculated from the ME data and
the single crystal X-ray data. From the Ғ values it is possible to
calculate the rmsav of the metal atom at all temperatures in the
accessible range, and this is shown in Fig. 11.
From this figure it will be noted that the temperature-
dependence of the rmsav of Fe2 of 6 is quite similar to that of
ferrocene, the small difference being presumably due to the ligation
of this moiety to the central Te atom. On the other hand, the rmsav
data of Fe1 and Fe3 of 6 (represented by the filled red (in the web
version) data points) are quite similar and significantly smaller than
the corresponding data for Fe2 reflecting a tighter binding of Fe1
and Fe3 than Fe2 in the compound 6. These data are also consistent
with the interatomic distance measurements extracted from the
single crystal X-ray data at 296 K and DFT simulated IS and QS
parameters for iron atoms in 6 (Table 2).
Conclusion
Although the introduction of the ferrocenyl group instead of the
phenyl group in the telluride compounds does not change signifi-
cantly the chemical properties and structures of the complexes, it
provides an opportunity to oxidize the ferrocenyl group in a one-
electron quasi-reversible process. The interaction of FcTeI with
Fig. 8. 57
Fe M€ossbauer spectrum of compound 6. The three Fe sites are assigned to Fe1
(blue), Fe2 (green) and Fe3 (red) following the notation of the single crystal X-ray
assignments. The hyperfine parameters (IS and QS), their temperature dependencies,
and the associated dynamical parameters are summarized in Table and further dis-
cussed in the text. (For interpretation of the references to color in this figure legend,
the reader is referred to the web version of this article.)
Fig. 9. The temperature-dependence of d ln(A(T)/A(90)]/dT for the Fe2 atom of com-
pound 6.
Table 1
Summary of the ME and related parameters for compound 6. The parenthetical
values are the errors in the last significant figure(s). The quadrupole parameters (QS)
are not temperature sensitive in the range 96 T 300 K of the ME measurements.
Fe1 Fe2 Fe3
IS(90) 0.187 (18) 0.494 (12) 0.148 (13) mm sÀ1
QS(90) 1.694 (14) 2.425 (8) 0.441 (9) mm sÀ1
Àd IS/dT 5.9 (10) 3.29 (10) 3.44 (88) Â10À4
mm s1
KÀ1
Àd ln [A(T)/A(90)] 4.95 (17) 6.20 (6) 11.54 (17) Â10À3
KÀ1
Meff 67 (7) 127 (4) 121 (25) Daltons
k2
xave
2
, X, 296 1.585 (8) 1.814 (9)
Fig. 10. The Ғ parameter for the Fe2 site of compound 6. The ME data are indicated by
the open data points, the value extrapolated to 0 K by the starred data point, and the
value calculated from the single crystal X-ray data by the filled data point.
Y.V. Torubaev et al. / Journal of Organometallic Chemistry 777 (2015) 88e9592
6. Fe(CO)5 proceeds as an oxidative addition, giving monomeric
(Fc2Te2)Fe(CO)3I2 and a dimeric complex [(CO)3IFe(m-TeFc)]2 .
CpFe(CO)2TeFc can substitute one CO group in Fe(CO)4I2 to give the
adduct CpFe(CO)2(m-TeFc)Fe(CO)3I2 and can then easily be haloge-
nated at the Te center by elemental bromine and iodine to give
monomeric CpFe(CO)2TeX2Fc (X ¼ Br or I). Alternatively the same
type of complexes arise when [FcTeI] is formally inserted into the
FceI bond of CpFe(CO)2I.
Experimental part
General procedure
All reactions and manipulations were performed using standard
Schlenk techniques under an inert atmosphere of pure nitrogen or
argon. Solvents were purified, dried and distilled under a nitrogen
atmosphere prior to use. Commercial Fe(CO)5, [CpFe(CO)2]2, I2, Br2
were used without additional purification. CpFe(CO)2I and
Fe(CO)4I2 were prepared following the reported procedure [13].
Diferrocenylditellurium (Fc2Te2) was prepared by a slightly modi-
fied procedure [14].
1
H, 13
C and 125
Te NMR spectra were recorded on Varian VXR-
300S and Bruker AVANCE III/400 spectrometer in CDCl3 with TMS
or Ph2Te2 as standards respectively at 293e295 K. Infrared spectra
were recorded on a Perkin Elmer FT-IR spectrometer as hexane
solutions in 0.1 mm path length NaCl cells. TLC plates were pur-
chased from Merck (20 Â 20 cm silica gel 60 F254).
Electrochemistry
The cyclic voltammograms (CV) of complexes 3 and 5 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 elec-
trochemical cell under a high purity argon atmosphere. An SU-2000
(0.0078 cm2
) glassy carbon disk pressed in Teflon served as the
working electrode and a platinum 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 sup-
porting electrolyte. The potential sweep rates were in the range
from 0.050 to 1.0 V sÀ1
.
M€ossbauer spectroscopy
The samples were transferred into plastic sample holders and
mounted in a variable-temperature cryostat as described previ-
ously [15]. The methods for spectrometer calibration, data analysis,
and temperature control monitoring have been detailed previously
[15]. All isomer shifts (IS) are given with respect to a room-
temperature a-Fe absorber spectrum which was also used for
spectrometer calibration. The ME spectral line widths for the
optically “thin” samples was 0.248 ± 0.013 mm sÀ1
DFT calculations
The M€ossbauer parameters were calculated at the DFT level of
theory using the ORCA program [16]. Scalar relativistic effects were
treated by the ZORA approximation [17,18]. Hybrid meta-GGA
functional TPSSh [19] was used with triple-z all electron relativ-
istic basis set recontracted for use with ZORA approximation (TZVP)
[20]. Isomer shifts were calculated from the electron density at
nuclei using a linear dependence d ¼ a(r À C) þ b with parameters
determined in Ref. [21]. Geometry of more populated isomer of
complex 7 was taken from XRD data and positions of hydrogen
atoms or all geometry parameters were optimized at TPSS [22]/
TZVP level of theory.
Synthesis of (CO)3FeI2(Fc2Te2) (1)
To the orange solution of Fc2Te2 (50 mg, 0.08 mmol) in CH2Cl2
(8 ml) violet solution of I2 (0.02 g, 0.08 mmol) in CH2Cl2 (3 ml) was
added and stirred for 30 min at 0 C. The resulting crimson-red
reaction mixture was treated with Fe(CO)5 (0.01 ml, 0.08 mmol)
and stirred for 3.5 h at 0 C, till the band of starting Fe(CO)5 dis-
appeared in the IR spectra. The reaction mixture was concentrated
with 2.5 ml of hexane (approx. to ½ of starting volume) filtered
and left for 24 h at À5 C to give a black prismatic crystalline
precipitate suitable for XRD study. Crystals were filtered off,
washed with hexane and dried in vacuum. An additional amount
of product was obtained from the dried mother-liquor. Yield:
0.038 g (47.5%)
IR spectra (KBr, nCO, cmÀ1
): 2079s, 2031s, 2026s.
Found (%): C 26.28H 1.94. For Fe3Te2I2H18O3C23 (Mr ¼ 1019)
Calc (%): C 27.11H 1.78
Synthesis of [(CO)3FeI(m-FcTe)]2 (2)
To the solution of diferrocenylditelluride (78 mg, 0.125 mmol)
and an equimolar amount of Iodine (I2) (0.032 g, 0.125 mmol) in
THF (10 mL), Fe(CO)5 (0.15 ml, 0.125 mmol) was added at room
temperature. The reaction mixture was stirred for 30 min. The
solvent was removed in vacuo, the residue was dissolved in
dichloromethane and subjected to chromatographic work-up using
TLC plates. Elution with a dichloromethane/hexane mixture
(20:80 v/v) gave Fc2TeI2 and 2. The single crystals of 2 suitable for
Fig. 11. The root-mean-square-amplitudes-of-vibration of the three Fe atoms in
compound 6 of the text. The data for Fe1 and Fe3 are essentially identical and differ
significantly for the values for Fe2. The comparison with the data for ferrocene (Fc) are
indicated by the filled black data points.
Table 2
Calculated IS and QS parameters for iron atoms in complex 6. Parameters calculated
for fully optimized geometry are given in parentheses.
Fe1 Fe2 Fe3
d, mm/s 0.10 (0.08) 0.48 (0.44) 0.05 (0.01)
DEQ, mm/s 1.69 (1.68) 2.41 (2.21) 0.18 (À0.29)
Y.V. Torubaev et al. / Journal of Organometallic Chemistry 777 (2015) 88e95 93
7. XRD investigation were obtained by recrystallization from CH2Cl2//
hexane mixture.
IR spectra (THF, nCO, cmÀ1
): 2057s, 2012s
Synthesis of CpFe(CO)2TeFc (3)
Red-brown mixture of 0.25 g (0.7 mmol) [CpFe(CO)2]2 and
0.44 g (0.7 mmol) Fc2Te2 in toluene (30 ml) was stirred at 100 C for
1 h. The resulting yellow-brown solution was filtered under argon,
concentrated under reduced pressure to 1/3 of its initial volume
and kept at À10 C for 24 h to provide a brown crystalline precip-
itate which contained crystals suitable for single-crystal X-ray
analysis. The crystals were decanted, washed with cold heptane
(2 Â 5 ml) and dried in vacuum. Yield: 0.6 g (87%)
Found (%): C 42.50H 3.05 For C17H24Fe2O2Te (Mr ¼ 489)
Calc. (%): C 41.70H 2.88.
IR spectrum (KBr; nCO, cmÀ1
): 1997, 1952.
1
H NMR (400 MHz, CDCl3) d 4.11 (m.br., 2H, C5H4Te), 4.18 (s, 5H,
C5H5), 4.29 (m.br., 2H, C5H4Te), 4.80 (s, 5H, C5H5). 13
C{H}
(100.6 MHz, CDCl3) 34.40, 70.00, 70.74, 80.15, 84,57, 215.31; 125
Te
NMR (126.2 MHz, CDCl3) d À407.7 (s, TePh).
Synthesis of CpFe(CO)2TeBr2Fc (4)
0.053 ml of Br2 was added to the stirred brown solution of 0.05 g
(0.1 mmol) CpFe(CO)2TeFc in CH2Cl2 (8 ml). The resulting red re-
action mixture was stirred at ambient temperature for 20 min and
filtered under argon. 2 ml of hexanes was added to the filtrate and
concentrated under reduced pressure to 1/2 of its initial volume
and kept at À10 C for 24 h to yield a red crystalline precipitate
which contained crystals suitable for single-crystal X-ray analysis.
Crystals were decanted, washed with cold heptane (2 Â 5 ml) and
dried in vacuum. Yield: 0.054 g (82%)
Found (%): C 31.477H 2.73. For CpFe(CO)2TeBr2Fc (Mr ¼ 650)
Calc. (%): C 31.44, H 2.17
IR spectrum (KBr; n, cmÀ1
): 2044, 1997.
Synthesis of CpFe(CO)2TeI2Fc (5)
a) To a solution of [FcTeI] formed at room temperature by
the reaction of diferrocenylditelluride, Fc2Te2 (78 mg,
0.125 mmol) with the equimolar amount of solid I2 (0.032 g,
0.125 mmol) in toluene (20 mL), cyclopentadienyliron dicar-
bonyl iodide [CpFe(CO)2I] (0.038 g, 0.125 mmol) was added.
The temperature was raised to 50
C and the reaction mixture
was stirred for 2 h. The mother liquor was decanted and the
dark-red precipitate was washed with hexane (15 ml) and
dried in vacuum. The single crystals suitable for XRD inves-
tigation were obtained by recrystallization from CH2Cl2//
hexane mixture.
Yield: 46 mg (49%).
b) The purple solution 0.025 g (0.1 mmol) of I2 in CH2Cl2 (2 ml) was
added to the stirred brown solution of 0.05 g (0.1 mmol)
CpFe(CO)2TeFc in CH2Cl2 (6 ml). The resulting red-brown reac-
tion mixture was stirred at ambient temperature for 30 min and
filtered under argon. 1.5 ml of hexanes was added to the filtrate,
concentrated under reduced pressure to 1/2 of its initial volume
and kept at À10
C for 24 h to provide a dark-red crystalline
precipitate which contained crystals suitable for single-crystal
X-ray analysis. Crystals were decanted, washed with cold hep-
tane (2 Â 5 ml) and dried in vacuum. Yield: 0.069 g (91%)
Found (%): C 27.73H 1.42 For CpFe(CO)2TeI2Fc (Mr ¼ 743)
Calc. (%): C 27.46H 1.89
IR spectrum (CH2Cl2; nCO, cМÀ1
): 2044, 2007.
Synthesis of CpFe(CO)2(m-TeFc)Fe(CO)3I2 (6)
At room temperature, a solution of 0.086 g (0.2 mM) Fe(CO)4I2 in
5 ml CH2Cl2 was added dropwise to the stirred solution of 0.1 g
(0.20 mM) CpFe(CO)2TeFc in 10 ml of CH2Cl2. The brown reaction
mixture was filtered, 2.5 ml of hexane was added and its volume
was reduced by 1/2 in vacuum. Being kept for 24 h at À10 C it
produced brown crystalline precipitate, containing crystals suitable
for single crystal XRD study, was decanted, washed with heptane
(2 Â 5 ml), and dried in vacuum.
Yield: 0.15 g (83%)
Found (%): C 27.57H 1.78 For C20H14O5Fe3TeI2 (Mr ¼ 883)
Calc. (%): C 27.20H 1.60.
IR spectra (KBr, n, cmÀ1
): 2072s, 2026s, 2008w, 1981w
Crystal structure determinations of compounds 1e6
Relevant crystallographic data and the details of measurements
for 1e6 are given in the online supplementary.
A Bruker APEX II CCD area detector diffractometer and CCD
Agilent Technologies (Oxford Diffraction) SUPER NOVA using
graphite-monochromated Mo Ka radiation (0.71070 Å) were used
for the cell determination and intensity data collection for com-
pounds 1, 3, 4, 6 and 2, 5 respectively.
The data were collected by the standard phi-omega scan tech-
niques, and were scaled and reduced using Bruker (for 1, 3, 4, 6) and
CrysAlisPro RED (for 2, 5) software packages.
Structures were solved by direct methods and refined by full-
matrix least squares (F2
) using SHELXL-97 [23] software. Except
for the carbon atoms of the disordered ferrocenyl Cp-rings in 1e3,
positions of non-hydrogen atoms were refined with anisotropic
thermal parameters. All hydrogen atoms were geometrically fixed
and refined using a riding model.
Acknowledgments
We gratefully acknowledge the financial support from the
Department of Science and Technology (DST, India), University
Grants Commission (UGC, India), Russian Foundation for Basic
Research (12-03-00860 and 13-03-92691), Department of Chem-
istry and Material Sciences of RAS (grant OKh 1.3), Presidium of RAS
(grant 8P23).
Appendix A. Supplementary material
CCDC nos. 1029846, 1029850, 1029851, 1029852, 1029853,
1029854 contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
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