F. Mathis

Influence de l'environnement moleculaire sur la frequence de vibration de valence Ge—H

Abstract The frequency of the Ge—H valence mode of vibration has been measured for about twenty alcoylgermanium hydrides and halogenohydrides. This frequency is raised by —I substituents on the Ge atom, and lowered by + I substituents. This substituent effect is additive and may be used for an estimation of inductive effect. The ν Ge—H frequency in R 1 R 2 R 3 GeH can be approximately related to the sum of Taft σ ∗ coefficients for R 1 , R 2 and R 3 by equation: v Ge—H (cm −1 ) = 2008 + 16·5 Σσ ∗ .

FROM ALLENIC PHOSPHORUS DERIVATIVES TO HETEROCYCLIC COMPOUNDS. SYNTHESIS OF A 1,2,3-DIAZAPHOSPHOLE COMPOUND WITH A STRONGLY POLAR NH GROUP LINKED TO A DICOORDINATE PHOSPHORUS ATOM

Abstract The synthesis of several derivatives containing an allenic group directly linked to a phosphoryl phosphorus atom is described. The addition of alcohol, water, hydrazines to this compounds is studied. The reaction of hydrazones (obtained from allenyldiphenylphosphine oxide) with trichlorophosphine gives rise to derivatives of 1,2,3-diazaphosphole. The hydrazone deriving from unsubstituted hydrazine leads to a compound with an NH group spectroscopically much more acidic than that of pyrrole; this NH group is presumably directly linked to the dicoordinated phosphorus atom.

Influence de l'environnement moléculaire sur la fréquence de vibration de valence Ge-H. Partie II

Abstract The frequency of the Ge-H valence mode of vibration has been measured for about thirty alkylgermanium hydrides, arylgermanium hydrides and alkyl (or aryl) germanium halogenohydrides. This frequency is raised by −I substituents bound to the germanium atom, and lowered by +I substituents; this effect is generally additive. However, there is, superimposed to it, a steric effect which is quite significant when several voluminous substituents are bound to the germanium atom. No large conjugation effect appears between the d orbital of Ge and the free doublets or π electrons of substituents.

Influence de l'environnement moléculaire sur la fréquence de vibration de valence GeH: Partie III. Influence des solvants

Resume The frequency of Ge-H valence mode of vibration has been measured for several compounds in a variety of solvents. The effect of medium on the frequency is generally slight. This seems to be due to the polarity Ge + H − of the GeH bond, which is unable to form a true hydrogen-bond with proton acceptors.

Etude de quelques composés cycliques polyfonctionnels renfermant le motif CONCO et de leurs dérivés phosphorylés. Liaisons hydrogène et spectres infrarouge

Resume The spectra of compounds containing a phosphoryl bond (P → O) and a heterocyclic ring containing the O  CNC  O system (phthalimide or hydantoin derivatives) have been studied both in the solid state and in various solvents. The spectra of the non phosphorus containing parent compounds are described for comparison. Several type of interactions occur: P → O … CO dipole interaction, NH … OC and NH … O ← P hydrogen bonding. The latter are dependent upon the nature of substituents linked to the phosphorus atom and on the steric requirements of the phosphorus moeity and of the heterocycle.

Vibrateur NH et activité antitumorale des cyclophosphazènes vectorisés par des polyamines biogènes

Abstract A comparative i.r. spectroscopic study of NH groups in natural polyamines both free and covalently bound to antitumor cyclophosphazenes allows one to explain the remarkable selectivity towards malignant cells of such drugs when vectorized through such polyamines as tumor finders and to classify the targeting potentiality of these polyamines as a function of the various configurations they adopt when linked to the cyclophosphazenic antitumor agents.

Spectres infrarouge et structure de composés cycliques azotés obtenus par l'action des hydrazines sur des derives d'hydrazonates et d'imidates

Abstract Hydrazine and monosubstituted derivatives thereof react with N -2 substituted hydrazonates to give pentagonal heterocyclic compounds: N -aminotriazolones from N -2 ethoxycarbonyl hydrazonates, N -aminotriazoles from N -2 acylhydrazonates. The action of hydrazines on N (methoxycarbonylmethyl) benzimidate leads to derivatives of 1,2,4-tetrazine.

The N–H link as a ‘probe’ for the electronic structure of the phosphorus–nitrogen bond in aminophosphines. An infrared spectroscopic study

Mechanical anharmonicity and hydrogen bond donor ability of the NH group in 26 aminophosphines X2P–NHR have been measured; large variations have been observed, which are related to the effect of substituents X on the s character of the nitrogen part of the NH bond orbital.

Spectres infrarouge d'oxydes d'allénylphosphines XYP(O)CHCCR1R2. Isomerie de rotation. Influence des substituants X et Y sur le dedoublement des bandes d'absorption du système allénique

Abstract Infrared spectroscopic study of compounds XYP(O)CHCCR 1 R 2 reveals the following facts: these compounds exhibit conformational isomerism, presumably arising from rotation about the PC(allenic) bond; the CCC “antisymmetric” stretching vibration frequencies are different for both isomers, and the difference can be correlated with the σ meta Hammett constants of substituents X and Y; the influence of the allenic group on the P → O stretching frequency cannot be entirely accounted for by purely inductive effect; this suggests that the phosphorus atom is in some way conjugated with the allenic system.

Pseudopotential calculations on aminophosphine H2P–NH2

The electronic structure of the H2P–NH2 molecule has been calculated using a pseudopotential method, considering independently the HNP and HNH, then the HPN and HPH angles; the optimized geometry corresponds to a gauche conformation in which the nitrogen atom is pyramidal (sum of bond angles 347°).