NMR spectroscopy and crystal structure of [Me2GaP(H)SitBu(3)](2) and theoretical investigations of the model compounds [R'2GaP(H)R'](2)

摘要

The dimeric phosphanylgallanes [R'2GaP(H)SitBu(3)](2) with R' = Me, Cl [Inorg. Chem. 43 (2004) 3756] were synthesized by metathesis reactions. The obtained compounds were characterized by NMR spectroscopy and single crystal X-ray crystallography. In order to compare the structures and to compare the relative energies of isomers, theoretical investigations were performed on the phosphanylgallane model compounds of the type [R'2GaP(H)R"](2) by using the hybrid density functional theory (B3LY-P). Different 1,3- and 2,4-substituted dimeric phosphanylgallanes with R' = Cl, Me, Et and R" = H, SiH3 and SiMe3 as well as their monomers were calculated and could be correlated to the cis-trans isomerization equilibrium constants which were accessible by integration of suitable P-31 NMR signals. (c) 2005 Elsevier B.V. All rights reserved.