After establishing some structural characteristics of a few simple AsR3*BH3 adducts (R = Me, Et, or Ph) by n.m.r. spectroscopy, the reaction of BH3 with a ligand (L) containing both phosphorus and arsenic donor sites (Ph,PCH,-CH,AsPh,) has been studied. The superior basicity of phosphorus as compared to arsenic in these adducts is shown by displacement reactions and a calorimetric study. Enthalpic data (in kJ mol-l) obtained for the gasliquid reactions (i) and ( ii) are AH1 = -1 60.4 and AH, = -1 53.4 for M = P, and AH1 = -76.1 and AH2 = -1 11.3 AH1 A H , 2MPh3(~0l) -I-B,H6 (9) + Z M P ~~* B H ~( S O I ) 0) MPhs(s01) + BH3 (9) MPh3*BH,(sol)(ii) for M = As. In the case of L, two stages of complexation may be separated and the corresponding enthalpies (kJ
EXPERIMENTALOwing to the sensitivity of the ligands and adducts to air, the experiments were made in a dry inert atmosphere.
ERA 31 5 BP 1044, Facult6 des Sciences, The 35CI n.q.r. frequencies observed in a series of solid chloromethylenedimethylammonium salts are in agreement with the general structure (i). The variations in the C -T I resonance frequency indicate a large polarisability
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