F.T. Delbeke

Transition metal chemistry: VIII. Synthesis and IR study of monosubstitution products of Cr(CO)6 and tertiary substituted aryl group VB derivatives

Abstract The synthesis of a series of compounds of general formula LCr(CO) 5 is presented, the ligands employeed being aryl Group VB derivatives of formuale (C 6 H 5 ) 3 E and ( 4- or 3-XC 6 H 4 ) 3 E with E = P, As, Sb and X = Cl, F. The ν(M—C) and δ(M—C—O) frequencies in the IR spectra have been assigned and are discussed. An assignment of the 12 CO 13 CO stretching fundamentals is also given. A possible explanation is presented for the anomalies observed in the ν(CO) spectrum and the CO frequency shifts are discussed in terms of σ and π bonding.

Organo group VB chemistry III. Synthesis and NMR spectra of some tertiary substituted arylstibines and arylbismuthines

An improved method for the synthesis of some stibines and bismuthines of the general formula (p-XC6H4)3E and (m-XC6H4)3E (X = Cl or F, E = Sb or Bi) is described. 1H and 19FSCENMR spectra are recorded for various compounds, and the results of a partial analysis of the NMR spectra are reported.

Transition metal chemistry III. A more exact method for evaluation of Co stretching force constants of pentacarbonyl complexes of transition metals, based on the cotton and kraihanzel force field

Within the framework of exact secular equations, a rigorous algebraic method for calculating all the CO stretching force constants of the complexes of general formula LM(CO)5 is possible yielding at once all the solutions, whether physically acceptable or not. This method does not imply interation and there is no need for estimating good initial approximations.

Transition metal chemistry V. Calculation of CO stretching force constants of cis disubstituted group VI metal carbonyls and (organo) group IV metal iron carbonyl complexes with lolca C2v symmetry

Abstract Using the Cotton and Kraihanzel force field, a more exact direct method is applied for calculating the CO stretching force constants of substituted metal carbonyls of general formula cis -L 2 M(CO) 4 (M = Mo, W, Cr; L = phosphine or amine) and of complexes of formula [R 2 MFe(CO) 4 ] 2 (M = Si, Ge, Sn or Pb),(R 3 Sn) 2 Fe(CO) 4 , R 4 M 3 [Fe(CO) 4 ] 4 (M = Sn or Pb) and M[Fe(CO) 4 ] 4 (M = Ge, Sn or Pb).

Transition metal chemistry: IX. Synthesis and IR study of Ni(CO)3L where L is a tertiary substituted aryl group VB derivative

The synthesis of a series of compounds of general formula LNi(CO)3 is presented, the ligands employed being aryl Group VB derivatives of formulae (C6H5)3E, (4-XC6H4)3E and E = P, As, Sb and X = Cl, F. The CO stretching frequencies and their shifts have been discussed for these compounds in terms of the σ bonding involved and a correlation between the CO force constants and the bonding suggests some interesting conclusions regarding the bonding in analogous LCr(CO)5 derivatives.

Transition metal chemistry IV. Calculation of force constants of substituted group VIIA metal carbonyls in the CO stretching region

Abstract A rigorous algebraic method, based on the Cotton and Kraihanzel force field, is presented for the direct calculation of CO stretching force constants of Group VIIA metal carbonyls of general formula [LM(CO) 4 ] 2 (M = Mn, Tc, Re; L a bridging ligand).

Transition metal chemistry : VII. Calculation of CO stretching force constants and separation of mesomeric and inductive effects for LM(CO)5 complexes

Abstract Refined values of the CO stretching force constants for monosubstituted metal pentacarbonyl complexes have been obtained by rigorous direct methods of calculation. The following compounds have been treated by this method: manganese carbonyl complexes, halogenometal pentacarbonyls, some recently prepared aminocarbene complexes [RHN(Me)C]Cr(CO) 5 , carbene pentacarbonyl compounds [R(OC 2 H 5 )C]M(CO) 5 (R = CH 3 , n-C 4 H 9 and M = Cr, W), phosphacarborane metal carbonyls of general formula (CH 3 ) 4 N[B 9 H 10 CHE M(CO) 5 ] with E = P, As and M = Mo, W, Cr and arsine pentacarbonyl complexes of Cr, Mo and W. Using the more exact carbonyl stretching force constants obtainable from such calculations, relative σ and π Graham parameters for a series of LMn(CO) 5 compounds have been derived. The relative importance of σ and π bonding in some organotin derivatives is discussed.

Organo-group vb chemistry I. Synthesis and nmr spectra of some tertiary substituted arylarsines and arsine oxides

Abstract Improved methods for the synthesis of some arsines of general formulate ( p -XC 6 H 4 ) 3 As and ( m -XC 6 H 4 ) 3 As (X = Cl, or F), and of their corresponding oxides, are described. The 1 H and 19 F NMR spectra are presented for some of these compounds, and the results of a partial analysis of the NMR spectra reported.

Transition metal chemistry VI. Calculation of force constants in the CO stretching region of cis-disubstituted group VI metal carbonyls and iron and carbonyl complexes with C2v symmetry

For complexes of the type cis-L2M(CO)4 (M = Mo, W, Cr; L = a phosphine, arsine or amine), (RHg)2Fe(CO)4 (R = Me, Bu) and (R3M)2Fe(CO)4 (M = Pb, Sn, Si or Ge) all the CO stretching force constants are calculated using a rigorous algebraic procedure based on the Cotton and Kraihanzel force field.

Organo-group vb chemistry II. Vibrational study of some tertiary substituted arylarsines and arsine oxides

Abstract The IR and Raman spectra of a series of arylarsines, (p-XC6H4)3 As and (m-XC6H4)3As(X=Cl, F), and of the corresponding oxides, measured over the spectral range 4000 and 100 cm−1, are reported. A complete vibrational analysis is presented.