173032-17-2Relevant academic research and scientific papers
Synthesis and nucleophilic behavior of cis-[M(C6F5)2(Ph2PCHPPh 2)]- (M = Pd, Pt): C-Alkylation, metalation, and halogenation of coordinated bis(diphenylphosphino)methane. X-ray crystal structure of [Pt(C6F5)2(Ph2PCHIPPh 2)]·C5H12
Falvello, Larry R.,Forniés, Juan,Navarro, Rafael,Rueda, Angel,Urriolabeitia, Esteban P.
, p. 309 - 316 (1996)
The reaction of the neutral complexes cis-[M(C6F5)2(Ph2PCH 2PPh2)] [M = Pd (1a), Pt (1b)] with LDA (lithium diisopropylamide) or LitBu (tert-butyllithium) in THF readily affords the anionic derivatives [M( C6F5)2(Ph2PCHPPh2)] - by deprotonation of the coordinated bis-(diphenylphosphino)methane (dppm). The reactivity of the carbanionic center thus generated toward a variety of substrates has been studied. The reaction with alkyl halides such as MeI or EtI gives the neutral, C-alkylated complexes cis-[M(C6F5)2(Ph2PCHRPPh 2)] [M = Pd, R = Me (2a), Et (4a); M = Pt, R = Me (2b), Et (4b)], and the reaction with ClAuPPh3 or O3ClOAgPPh3 gives the heterobimetallic species cis-M(C6F5)2[Ph2PCH(M′PPh 3)PPh2] [M = Pd, M′ = Au (5a) Ag (6a); M = Pt, M′ = Au (5b), Ag (6b)], in which the [Ph2PCHPPh2]- ligand acts as a bridging, tridentate-P,P′,C ligand. The reactions with halogens (Cl2, Br2, I2) or pentafluorophenyl halides (BrC6F5, IC6F5) produce the heterolytic cleavage of the X-X or X-C bond, giving the halogenated derivatives cis-[M(C6F5)2(Ph2PCHXPPh 2)] [M = Pd, X = I (9a); M = Pt, X = Cl (Tb), Br (8b), I (9b)]. The reaction of [Pt(C6F5)2(Ph2PCHPPh 2)]-with C6F5CN occurs with C-F bond cleavage, and the para-substituted product M(C6F5)2[Ph2-PCH(C6F 4CN-4)PPh2] (10b) is obtained. The X-ray crystal structure of 9b·C5H12 is reported.
