DONOR ACCEPTOR REACTIONS OF TITANIUM TETRACHLORIDE WITH FORMAMIDE AND N,N-DIMETHYL FORMAMIDE

1958 ◽  
Vol 36 (11) ◽  
pp. 1461-1466 ◽  
Author(s):  
Jacques Archambault ◽  
Roland Rivest
Keyword(s):  
Infrared Spectra ◽  
Titanium Tetrachloride ◽  
Dimethyl Formamide ◽  
Positive Shift ◽  
Negative Shift ◽  
Structural Formulas ◽  
Donor Acceptor

Co-ordination complexes of titanium tetrachloride with formamide and N,N-dimethyl formamide have been prepared. All the complexes found are explained through a co-ordination number of 6 for titanium (IV).The infrared spectra of these compounds were measured; a negative shift observed for the carbonyl frequency and a positive shift observed for what is thought to be the C—N frequency are explained by a co-ordination through the oxygen of these molecules. Structural formulas are proposed for the compounds obtained.

CO-ORDINATION COMPLEXES OF TITANIUM (IV) HALIDES: 1. PREPARATION AND INFRARED SPECTRA OF THE COMPLEXES OF TITANIUM (IV) HALIDES WITH N,N-DIMETHYL AND N,N-DIPHENYL FORMAMIDE

1960 ◽  
Vol 38 (8) ◽  
pp. 1331-1338 ◽  
Author(s):  
Jacques Archambault ◽  
Roland Rivest
Keyword(s):  
Double Bond ◽  
Carbonyl Group ◽  
Infrared Spectra ◽  
Dimethyl Formamide ◽  
Double Bond Character ◽  
Positive Shift ◽  
Negative Shift ◽  
Oxygen Bond ◽  
Bond Character

Co-ordination complexes of titanium (IV) halides with N,N-dimethyl formamide and N,N-diphenyl formamide have been prepared and their infrared spectra have been measured. In all these complexes, there is a metal-to-oxygen bond as evidenced in the infrared spectra by a negative shift of the carbonyl stretching frequency and a positive shift of the CN stretching frequency. The relative values of these shifts and the ease of decomposition observed for these complexes indicate that their stability decreases with decreasing the electronegativity of the halide bonded to titanium (IV).In the complexes of N,N-diphenyl formamide, the effect of the conjugated phenyl groups has been observed. In these complexes the decrease of double-bond character of the carbonyl group and the increase of double-bond character of the CN group, resulting from the metal-to-oxygen co-ordination bond, are quite larger than in the complexes of N,N-dimethyl formamide.

CO-ORDINATION COMPLEXES OF TITANIUM (IV) HALIDES: II. PREPARATION AND INFRARED SPECTRA OF THE COMPLEXES OF TITANIUM TETRACHLORIDE WITH DIESTERS OF α,ω-DICARBOXYLIC ACIDS AND COMPARISON WITH ANALOGOUS COMPLEXES OF ZIRCONIUM TETRACHLORIDE AND TIN TETRACHLORIDE

1961 ◽  
Vol 39 (11) ◽  
pp. 2343-2352 ◽  
Author(s):  
Ernest Rivet ◽  
Real Aubin ◽  
Roland Rivest
Keyword(s):  
Molecular Weight ◽  
Infrared Spectra ◽  
Titanium Tetrachloride ◽  
Complex Molecule ◽  
Dicarboxylic Acids ◽  
The Other ◽  
Zirconium Tetrachloride ◽  
Melting Points ◽  
Zirconium Complexes ◽  
Tin Tetrachloride

Co-ordination complexes between diesters of α,ω-dicarboxylic acids and titanium tetrachloride, tin tetrachloride, and zirconium tetrachloride have been prepared. The analytical results, the infrared spectra, the melting points, and the molecular-weight determinations indicate that for the titanium and zirconium complexes, two types of complexes are obtained, one having a general formula MX4•1 diester in which chelate rings from five to nine atoms are formed and the other one, 2MX4•1 diester in which there are two 4-membered rings per complex molecule. With tin tetrachloride only one type of complex is formed, which has two tin tetrachlorides and two diesters per complex molecule.

Synthesis, spectral and electrochemical study of coordination molecules Cu4OX6L4: 4-cyanopyridine Cu4OBrnCl(6−n)(4-CNpy)4 complexes

2010 ◽  
Vol 64 (3) ◽  
Author(s):  
Gregor Ondrejovič ◽  
Adela Kotočová ◽  
Marian Koman ◽  
Peter Segľa
Keyword(s):  
Cyclic Voltammetry ◽  
Infrared Spectra ◽  
Electronic Spectra ◽  
Pyridine Ring ◽  
Pyridine Complexes ◽  
Half Wave ◽  
Out Of Plane ◽  
Donor Acceptor ◽  
Back Bonding ◽  
Stretching Vibrations

AbstractNew 4-cyanopyridine halide and mixed-halide Cu4OBrnCl(6−n)(4-CNpy)4 complexes (4-CNpy = 4-cyanopyridine, n = 0–6) were synthesised, characterised, and studied by infrared spectra, electronic spectra, and cyclic voltammetry. Infrared spectra revealed donor-acceptor vibrational couplings of the Cu4O, Cu-Cl, and Cu-N stretching vibrations with the in-plane and out-of-plane pyridine ring vibrations. The infrared spectra, electronic spectra, and half-wave potentials correspond to a weak donor and a strong acceptor behaviour of the 4-cyanopyridine ligands and to π-back bonding, Cu(II)→pyridine rings. The results were compared with the related pyridine and 4-substituted pyridine complexes.

Vibrational spectroscopic studies and normal coordinate analyses of TiCl4 donor-acceptor complexes

1974 ◽  
Vol 27 (9) ◽  
pp. 1855 ◽  
Author(s):  
RP Cooney ◽  
DB Fraser
Keyword(s):  
Raman Spectrum ◽  
Spectral Data ◽  
Infrared Spectra ◽  
Spectroscopic Studies ◽  
Normal Coordinate ◽  
Laser Raman ◽  
Laser Raman Spectra ◽  
Donor Acceptor ◽  
Nitrogen Heteroatom ◽  
Octahedral Configuration

Laser Raman spectra and infrared spectra are reported for TiCl4,2MeCN, TiCl4,2PhCN, TiCl4,2py, TiBr4,2MeCN. For purposes of comparison the Raman spectrum of SnC14,2Ph3P has been recorded and assigned. Analysis of data indicates that a cis octahedral configuration is adopted by the TiC14,2L complexes and a trans configuration by SnCl4,2Ph3P. In addition a new complex, 3TiC14,4cpy, has been prepared and spectral data indicate the ligand bonds through its nitrogen heteroatom. Normal coordinate analyses and Urey-Bradley force constants are reported for TiC14,2MeCN and TiCl4,- 2PhCN.

CO-ORDINATION COMPLEXES OF GROUP (IV) HALIDES: PREPARATION AND INFRARED SPECTRA OF THE CO-ORDINATION COMPOUNDS OF TITANIUM TETRACHLORIDE, TITANIUM TETRABROMIDE, ZIRCONIUM TETRACHLORIDE, TIN TETRACHLORIDE, AND BORON TRICHLORIDE WITH ETHYL CYANOACETATE AS LIGAND

1964 ◽  
Vol 42 (5) ◽  
pp. 1079-1083 ◽  
Author(s):  
Sumer Chand Jain ◽  
Roland Rivest
Keyword(s):  
Infrared Spectra ◽  
Titanium Tetrachloride ◽  
Ethyl Cyanoacetate ◽  
Group Iv ◽  
Membered Ring ◽  
Zirconium Tetrachloride ◽  
Experimental Conditions ◽  
Boron Trichloride ◽  
Titanium Tetrabromide ◽  
Tin Tetrachloride

Co-ordination compounds between ethyl cyanoacetate and boron trichloride, titanium tetrabromide, and tetrachlorides of titanium, zirconium, and tin have been prepared. The analytical results indicate that under similar experimental conditions, 1:1 addition compounds are obtained in each case. On the basis of infrared spectra it has been postulated that the compounds obtained are six-membered ring chelates, satisfying the most common co-ordination number six for the elements of group IV.

COORDINATION COMPLEXES OF TITANIUM (IV) HALIDES: IV. PREPARATION AND INFRARED SPECTRA OF THE COMPLEXES OF TITANIUM TETRACHLORIDE WITH CHLORINE-SUBSTITUTED ESTERS OF MONOBASIC ACIDS AS LIGANDS

1962 ◽  
Vol 40 (12) ◽  
pp. 2243-2248 ◽  
Author(s):  
Sumer Chand Jain ◽  
Roland Rivest
Keyword(s):  
Infrared Spectra ◽  
Alkyl Radical ◽  
Titanium Tetrachloride ◽  
Coordination Complexes ◽  
Melting Points ◽  
Ether Group ◽  
Basic Properties ◽  
Acid Radical ◽  
Chlorine Substitution ◽  
Coordination Bonds

Coordination complexes between titanium tetrachloride and some chlorine-substituted monoesters have been prepared.Infrared spectra of these complexes and their melting points indicate that the strength of the coordination bonds decreases as the number of chlorines increases in the acid radical. When the substitution is in the alkyl radical, it is possible to prepare complexes of the formula TiCl4•2 ester, since the chlorine substitution decreases the basic properties of the oxygen of the ether group in the ligand.

COORDINATION COMPLEXES OF TITANIUM (IV) HALIDES: III. PREPARATION AND INFRARED SPECTRA OF THE COMPLEXES OF TITANIUM TETRACHLORIDE WITH UREA, THIOUREA, AND SOME OF THEIR DERIVATIVES

1962 ◽  
Vol 40 (12) ◽  
pp. 2234-2242 ◽  
Author(s):  
Roland Rivest
Keyword(s):  
Molecular Weight ◽  
Oxygen Atom ◽  
Infrared Spectra ◽  
Titanium Tetrachloride ◽  
Coordination Complexes ◽  
Dinuclear Complexes ◽  
Derivatives Of

The following coordination complexes of titanium (IV) have been prepared: TiCl4•2CO(NH2)2, TiCl4•CO(NHCH3)2, TiCl4•2CO(NHCH3)2, 2TiCl4•2NH2CON(C6H5)2, 2TiCl4•2CO(NHC6H5)2 TiCl4•2CS(NH2)2, 2TiCl4•CS(NHC2H5)2, 2TiCl4•NH2CSN(C6H5)2, and 2TiCl4•CS(NHC6H5)2; their infrared spectra have been measured and their molecular weight determined. For urea and its derivatives the coordination to titanium (IV) is always through the oxygen atom. The phenyl derivatives of urea led to dinuclear complexes which were best explained by assuming halogen bridging between the titanium atoms. Thiourea and its derivatives gave complexes in which coordination occurred through one of the nitrogens in the case of thiourea and through both nitrogens in the case of the derivatives. Halogen bridging was again assumed to explain the formation of the dinuclear complexes.

Dimethyl and diphenyl formamide complexes of lanthanide perchlorates

1969 ◽  
Vol 47 (6) ◽  
pp. 995-999 ◽  
Author(s):  
S. S. Krishnamurthy ◽  
S. Soundararajan
Keyword(s):  
Molecular Weight ◽  
Infrared Spectra ◽  
Spectral Studies ◽  
Dimethyl Formamide ◽  
Oxygen Conductivity ◽  
Coordination Numbers ◽  
Lanthanide Perchlorates

N,N-Dimethyl formamide (DMF) and N,N-diphenyl formamide (DPF) complexes of six lanthanide perchlorates of the composition M(DMF)8(ClO4)3 and M(DPF)6(ClO4)3 where M = La, Ce, Pr, Nd, Sm, or Y have been prepared and characterized. The infrared spectra show that the amide is bonded to the metal through oxygen. Conductivity, molecular weight, and spectral studies indicate coordination numbers of eight and six for DMF and DPF complexes respectively, with the perchlorate groups remaining ionic.

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