28310-00-1Relevant academic research and scientific papers
Bismuth-halide oxidative addition and bismuth-carbon reductive elimination in platinum complexes containing chelating diphosphine ligands
Nabavizadeh, S. Masoud,Niroomand Hosseini, Fatemeh,Nejabat, Negar,Parsa, Zahra
, p. 13480 - 13489 (2014/01/06)
Reaction of BiX3 (X = Cl, Br, I) with [PtMe2(P-P)], (1a, P-P = dppm; 1b, P-P = dppe), occurs easily to yield a mixture of platinum(II) complexes [PtMeX(P-P)], 2, and [PtX2(P-P)], 3, and the binuclear complex [Pt2Me2(μ-X)(μ-dppm) 2]X, 4. On the basis of 31P NMR and UV-vis spectroscopy, a mechanism is proposed in which the rate determining step is conversion of the yellowish Pt(II)-BiX3 adduct BiI3·[PtMe 2(dppm)], A, into the Pt(IV)-Bi(III) intermediate [PtMe 2(BiX2)X(P-P)], IM1. Density functional theory (DFT) studies suggest that intermediate IM1 may be formed in acetone solution which undergoes the Bi-C reductive elimination process before formation of complexes 2 and 3. The structures of intermediates IM1 were theoretically determined using DFT calculations. In dilute acetone solution, as monitored by UV-vis spectroscopy, the oxidative addition processes follow first order kinetics. The overall reaction is slower for heavier halide.
Tin(II) halide insertion or halogen exchange in the reactions of dihaloplatinum(II) complexes with tin(II) halide
Momeni, Badri Z.,Kazmi, Hoori,Najafi, Atefeh
, p. 1618 - 1627 (2011/10/31)
Reactions of SnCl2 with the complexes cis-[PtCl 2(P2)] (P2=dppf (1,1′- bis(diphenylphosphino)ferrocene), dppp (1,3-bis(diphenylphosphino)propane=1, 1′-(propane-1,3-diyl)bis[1,1-diphenylphosphine]), dppb (1,4-bis(diphenylphosphino)butane=1,1′-(butane-1,4-diyl)bis[1, 1-diphenylphosphine]), and dpppe (1,5-bis(diphenylphosphino)pentane=1,1′- (pentane-1,5-diyl)bis[1,1-diphenylphosphine])) resulted in the insertion of SnCl2 into the Pt-Cl bond to afford the cis-[PtCl(SnCl 3)(P2)] complexes. However, the reaction of the complexes cis-[PtCl2(P2)] (P2=dppf, dppm (bis(diphenylphosphino)methane=1,1′-methylenebis[1,1-diphenylphosphine]), dppe (1,2-bis(diphenylphosphino)ethane=1,1′-(ethane-1,2-diyl)bis[1,1- diphenylphosphine]), dppp, dppb, and dpppe; P=Ph3P and (MeO) 3P) with SnX2 (X=Br or I) resulted in the halogen exchange to yield the complexes [PtX2(P2)]. In contrast, treatment of cis-[PtBr2(dppm)] with SnBr2 resulted in the insertion of SnBr2 into the Pt-Br bond to form cis-[Pt(SnBr3) 2(dppm)], and this product was in equilibrium with the starting complex cis-[PtBr2(dppm)]. Moreover, the reaction of cis-[PtCl 2(dppb)] with a mixture SnCl2/SnI2 in a 2 : 1 mol ratio resulted in the formation of cis-[PtI2(dppb)] as a consequence of the selective halogen-exchange reaction. 31P-NMR Data for all complexes are reported, and a correlation between the chemical shifts and the coupling constants was established for mono- and bis(trichlorostannyl) platinum complexes. The effect of the alkane chain length of the ligand and SnII halide is described. Copyright
Synthesis and structure of gold and platinum menthyl complexes
Zuzek, Ashley A.,Reynolds, Samantha C.,Glueck, David S.,Golen, James A.,Rheingold, Arnold L.
, p. 1812 - 1817 (2011/05/12)
A Grignard reagent derived from (-)-menthyl chloride has been reported to be a 1:1 mixture of menthyl magnesium chloride and neomenthyl magnesium chloride, which do not interconvert. Addition of an excess of this reagent to Au(PPh3)(Cl) or Pt(dppe)Cl2 gave Au(PPh3)(Men) (1) and Pt(dppe)(Men)(Br) (2), respectively. Crystallographic studies of these first well-characterized transition metal menthyl complexes showed that the menthyl group adopts a conformation with all three substituents in equatorial positions. NMR spectroscopic data for 2 showed that menthyl has a large trans influence, comparable to other alkyl groups. Decomposition of 1 in CDCl 3 gave Au(PPh3)(Cl) and a mixture of menthyl chloride and neomenthyl chloride, while 2 formed the halide complexes Pt(dppe)Cl2, Pt(dppe)Br2, and Pt(dppe)(Br)(Cl) and a mixture of 2-menthene and 3-menthene.
Aryl-halide versus aryl-aryl reductive elimination in Pt(IV)-phosphine complexes
Yahav-Levi, Anette,Goldberg, Israel,Vigalok, Arkadi
, p. 8710 - 8711 (2007/10/03)
Upon the addition of Br2 to complexes (P-P)Pt(Ar)2, two different products were observed, depending on the bite angle of the bidentate phosphine ligand: a Pt(II) aryl bromide complex, the product of C-Br reductive elimination, and Pt(IV) oxidative addition complex. At high temperatures, the latter exclusively gave the product of the C-C reductive elimination. Copyright
