859527-89-2Relevant academic research and scientific papers
Unexpected formation of polydentate phosphinoalkyl-silyl and -germyl ligands from reaction of [MoH4(Ph2PCH2CH 2PPh2)2] with organosilanes and organogermanes: Novel activation of Mo-H, E-H (E = Si, Ge), and C-H bonds in the same system
Minato, Makoto,Zhou, Da-Yang,Zhang, Li-Bin,Hirabayashi, Ryo,Kakeya, Masaki,Matsumoto, Takaomi,Harakawa, Akifumi,Kikutsuji, Gosuke,Ito, Takashi
, p. 3434 - 3441 (2005)
Reaction of [MoH4(Ph2PCH2CH 2PPh2)2] (1) with PhEH3 (E = Si, Ge) in refluxing toluene yielded the novel complexes [MoH3{[Ph 2PCH2CH2P(Ph)C6H4-o] 2(Ph)E-P,P,P,P,E}] (E = Si (2), Ge (3)) with a quinquidentate ligand comprised of a P-P-E-P-P framework as a result of the oxidative addition involving E-H bond cleavage with concomitant selective activation of the ortho C-H bonds of the two dppe ligands. When secondary Ph2SiH2 was employed in a similar reaction with 1, a trihydrido complex with a tridentate ligand ([Ph2PCH2CH2P-(Ph)C 6H4-o]Ph2Si-P,P,Si) comprised of a P-P-Si framework was isolated. On the other hand, the reaction between Ph 2GeH2 and 1 proceeded with accompanying evolution of 1 mol of benzene to give 3; that is, in addition to the Ge-H and C-H activation, Ge-C(Ph) bond cleavage took place. It is concluded that the reaction path includes the intermediacy of silylene or germylene metal complexes via an α-migration process on the basis of deuterium-labeling studies.
