Boron trifluoride and boron trichloride addition compounds of trimethylphosphine, chlorodimethylphosphine, dichloromethylphosphine and phosphorus trichloride

MARKHAM, ROY T.; Dietz, Edward A.; Martin, Donald S.

doi:10.1016/0022-1902(74)80103-x

Cited by 10 publications

(1 citation statement)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The set of trimethylphosphine complexes is a representative example in case: While the adducts with BCl 3 , BBr 3 and BI 3 could be crystallized and their structures determined, the BF 3 adduct was found to undergo rapid dissociation into its components on attempted crystallization. [24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42] It is therefore the more noteworthy that in the present work crystallization of the homologous (Et 3 P)BF 3 was successful.…”

Section: Introductionmentioning

confidence: 80%

Trivinylphosphineborane (CH2CH)3PBH3 and related compounds

2003

View full text Add to dashboard Cite

In an investigation of the vinyl-activation in trivinylphosphine by acceptor molecules the 1 : 1 addition compounds with BH 3 , BCl 3 , BBr 3 , and BI 3 have been prepared. The reaction of Vi 3 P with BF 3 led to polymerization of the phosphine and its adduct. While the complexes (Vi 3 P)BX 3 with X = Cl, Br and I are air-stable colorless crystalline solids, (Vi 3 P)BH 3 is a colorless, distillable liquid. The NMR spectra show little variation in the chemical shifts and coupling constants of the nuclei of the vinyl groups with the nature of the halogen, but there are large differences as compared to the borane complex (X = H). The crystal structures of the three boron trihalide complexes are also very similar. The components Vi 3 P and BX 3 have a staggered conformation and the vinyl groups are in an all-trans propeller orientation. The variations in the bond distances and angles are very small and do not indicate major trends within the series. As shown by the successful preparation and structure elucidation of the reference compound (Et 3 P)BF 3 , the instability of (Vi 3 P)BF 3 is not due to an intrinsically low affinity of BF 3 to tertiary phosphines or a steric effect of the phosphine. (Et 3 P)BF 3 has an exceedingly long P-B donor-acceptor bond. It appears that BF 3 forms a weak complex, but is most effective in activating the vinyl groups for polymerization. In (Vi 3 P)BH 3 the three vinyl groups and the three B-H function would match for an intermolecular triple-hydroboration to give a three-dimensional polymer with C-C and P-B structural units, but neither of the two functionalities appears to be sufficiently activated to accomplish this reaction.

show abstract