31277-98-2Relevant articles and documents
Chiral platinum duphos terminal phosphido complexes: Synthesis, structure, phosphido transfer, and ligand behavior
Scriban, Corina,Glueck, David S.,DiPasquale, Antonio G.,Rheingold, Arnold L.
, p. 5435 - 5448 (2006)
Treatment of Pt halide precursors with the secondary phosphine PHMe(Is) in the presence of the base NaOSiMe3 gave the terminal phosphido complexes Pt(Duphos)(Ph)(PMeIs) (Is = 2,4,6-(i-Pr)3C 6H2, Duphos = (R,R)-Me-Duphos (1), (R,R)-i-Pr-Duphos (2)), Pt((R,R)-Me-Duphos)(X)(PMeIs) (X = I (3), Cl (4)), and Pt((R,R)-Me-Duphos) (PMeIs)2 (5). Low-barrier pyramidal inversion in the phosphido complexes was investigated by 31P NMR spectroscopy. Protonation of 1-5 with HBF4 gave the secondary phosphine complexes [Pt(Duphos)(Ph)(PHMeIs)][BF4] (Duphos = (R,R)-Me-Duphos (6), (R,R)-i-Pr-Duphos) (7)), [Pt((R,R)-Me-Duphos)(X)(PHMeIs)][BF4] (X = I (8), Cl (9)), and [Pt((fl,/?)-Me-Duphos)(PHMeIs)2][BF 4]2 (10); cations 6, 9, and 10 were prepared independently from Pt chloride precursors using Ag(I) salts and PHMe(Is) and then deprotonated to yield phosphido complexes 1-5. Oxidation of the phosphido ligands in 4 and 5 with H2O2 gave Pt((R,R)-Me-Duphos)(Cl) (P(O)MeIs) (11) and Pt((R,R)-Me-Duphos)(P(O)-MeIs)2 (12), respectively. Complexes 1-6, 9, and 11 were structurally characterized by X-ray crystallography; structural and 31P NMR results suggest the trans influence order P(O)MeIs > PMeIs > PHMe(Is). Reaction of 1 with [Pd(allyl)Cl]2, followed by treatment with dppe, gave Pt((R,R)-Me-Duphos)-(Ph)(Cl), PMeIs(allyl) (13), and Pd(dppe)2. Treatment of 1 with Pd(P(o-Tol)3)2 gave an equilibrium mixture containing the two-coordinate palladium complex Pd(P(o-Tol) 3)(μ-PMeIs)Pt((R,R)-Me-Duphos)(Ph) (14), Pd(P(o-Tol) 3)2, P(o-Tol)3, and 1.
Transition metal chemistry of low valent group 13 organyls
Gemel, Christian,Steinke, Tobias,Cokoja, Mirza,Kempter, Andreas,Fischer, Roland A.
, p. 4161 - 4176 (2007/10/03)
The coordination of low-valent group 13 organyls EIR [E = Al, Ga, In; R = Cp*, C(SiMe3)3] to transition metals has attracted increasing interest over the past decade. Complexes and cluster compounds of these new ligands with a number of transition metals have been isolated and characterised. The EIR moiety is formally isolobal with CO and PR3 (R = alkyl, Cp*) or carbenes (R = chelating group) with varying σ-donor and π-acceptor properties depending on the organic group R as well as the group 13 metal E. In this review, different ways of forming M-E bonds such as substitution reactions of labile ligands or insertion of EIR into transition metal halide bonds are described. Furthermore, the reactivity of homoleptic complexes Ma(EIR) b, is discussed, outlining the use of these new complex types in bond activation reactions. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
Taking too many precautions in making a catalyst is never a loss of time: A lesson we learned at our own expense
Bianchini, Claudio,Meli, Andrea,Oberhauser, Werner
, p. 4281 - 4285 (2008/10/08)
The reaction in MeOH between the bis-chelate complex [Pd(dppe)2](OAc)2 and Pd(OAc)2 to give the monochelate product Pd(OAc)2(dppe) is assisted by free acetate ion, and its rate is proportional to the concentrations of both reagents (dppe = 1,2-bis(diphenylphosphino)-ethane). The aggregation of Pd(OAc)2 in CH2Cl2 and the low dielectric constant of this solvent are proposed to be important factors in accelerating the formation of Pd(OAc)2(dppe) in CH2Cl2.