R. F. De Ketelaere

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.

Organophosphorus chemistry: Part IV. Vibrational spectroscopic study of the PO, PS and PSe bonds in triarylphosphorous chalcogenides

Abstract The infrared and Raman spectra of the series (4-XC6H4)3-n(C6H5)nPY, (3-XC6H4)3-n (C6H5)nPY (X = Cl or F, n = 0,1,2) and (4-FC6H4)3-n (3-FC6H4)nPY (n = 1,2) (Y = O, S and Se) compounds have been studied and assignments for the v(P=O), v(P=S) and v(P=Se) stretching frequencies are proposed. The results indicate that the frequency shifts caused by the substituents bonded to phosphorus are more important in the PS and PSe bond than in the PO bond. Mechanisms for the changes in PY bond order as a result of changing the aromatic substituent are 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.

Organo group VB chemistry: Part IV: on the NQR spectra of tertiary aryl group VB compounds (35Cl, 75As, 121Sb, 209Bi)

Abstract The NQR spectra for the nuclei 35 Cl, 75 As, 121 Sb/ 123 Sb and 209 Bi at 300°K in the series of compounds (4-XC 6 H 4 ) 3 M and (3-XC 6 H 4 ) 3 M (M = P, As, Sb, Bi; X = H, F, Cl) are measured. Hammet sigma constants are calculated. The bonding in these molecules is discussed.

Organo group VB chemistry: Part VI. On the electric dipole moments of some substituted tertiary phenylphosphines, -arsines, -stibines and -bismuthines

Abstract The dipole moments of the following series of tertiary substituted aryl-group VB compounds were measured: ( a ) (C 6 H 5 ) 3 M and (XC 6 H 4 ) 3 M with M = P, As, Sb, Bi and X = 4-F, 4-Cl, 4-CH 3 , 3-F, 3-Cl; and ( b ) (3-XC 6 H 4 ) 3− n PR n with R = C 6 H 5 , 4-FC 6 H 4 and X = F, Cl. These experimental molecular moments are discussed as a consistent set of data that allows the calculation, within the framework of the vectorial additive method, of suitable group moments, bond moments and configurational parameters.

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.

Organo group VB chemistry : IV. vibrational study of some tertiary substituted aryl-group VB compounds

Abstract The IR and Raman spectra of a series para - and meta -substituted aryl-Group VB compounds (XC 6 H 5 ) 3 M (X = Cl, F) (M = P, As, Sb, Bi) measured over the spectral range 4000 to 100 cm -1 , are reported. The results of a complete vibrational analysis are used to discuss the identification of the products. The shifts of substituent-sensitive vibrations are discussed.

Organophosphorus chemistry: Part V. 1H NMR spectroscopy of triply and quadruply coordinated phosphorus compounds

Abstract The 1 H NMR spectra of a series of substituted aryl-phosphorus derivatives R 3 P, R 3 PO, R 3 PS and R 3 PSe (R = 4-FC 6 H 4 , 4-C1C 6 H 4 , 3-FC 6 H 4 , and 3-C1C 6 H 4 ) were measured. It is shown that the 1 H shift of the protons on the ring is predominantly influenced by the nearest neighbour substituent of the respective protons. Furthermore the spin-spin coupling constant J p-h increases when the valence angle increases.