67477-87-6Relevant academic research and scientific papers
Trimethylsilyl halide adducts of dinuclear phosphine-bridged palladium halide complexes: Synthesis, spectroscopy, and reactions of Pd2X2(dppm)2·Me3SiX′ (X, X′ = Cl, Br, I)
Kirss, Rein U.
, p. 3451 - 3458 (2008/10/08)
Reaction of Pd2X2(dppm)2 (1, X = Cl; 2, X = Br; 3, X = I) with Me3SiX′ (X′ = Cl, Br, I) in dichloromethane produced transient dark green solutions for all combinations of X and X′ with the exception of X = X′ = Cl. Net halide exchange was observed for reactions of 1 with Me3SiBr or Me3SiI and for 2 with Me3SiI, apparently without oxidative addition of the silicon-halide bond. Mono- and dinuclear palladium complexes Pd2(μ-CH2)Cl2(dppm)2 (4) and PdCl2(dppm) (5) also exchanged Pd-Cl bonds for Pd-Br bonds in reactions with Me3SiBr. Low-temperature 1H and 31P NMR spectroscopy provided evidence for formation of adducts of formulas Pd2Cl2(dppm)2·Me3-SiCl, Pd2Br2(dppm)2·Me3SiCl, Pd2Br2(dppm)2·Me3SiBr, Pd2I2(dppm)2·Me3SiBr, and Pd2I2(dppm)2·Me3SiI in the reactions of 1-3 with Me3SiX′. Dark green solids of formula Pd2X2(dppm)2·Me3SiX′ (6: (a) X = Cl, X′ = I; (b) X = Br, X′ = I; (c) X = Br, X′ = Br; (d) X = Cl, X′ = Br; (e) X = I, X′ = Br; (f) X = I, X′ = I) could be isolated from the reaction mixtures. The green color is proposed to result from a weakening of the metal-metal bond in 1-3 upon coordination of the trimethylsilyl halide. The presence of oxygen in reactions of 1-3 with Me3SiX′ (X = Cl, Br, I) did not interfere with the formation of the adduct but led to the formation of siloxanes and mononuclear palladium complexes PdXX′(dppm). There was no evidence for Si-Si bond formation in these systems. Halide exchange was also observed in reactions of 1, 2, and 5 with methyl iodide.
The Synthesis and Reactions of Palladium-Iron Carbonyl Complexes containing Bridging Ph2PCH2PPh2 Ligands
Jacobsen, Grant B.,Shaw, Bernard L.
, p. 2005 - 2008 (2007/10/02)
Treatment of tetrahydrofuran solution of FeI2 with two equivalents of Ph2PCH2PPh2 (dppm),under an atmosphere of CO, gave trans,mer-2(CO)(dppm-PP')(dppm-P)> (1b) in high yield.The bromide analogue
Novel reactions of metal-metal bonds. Reactions of Pd2{(C6H5)2PCH2P(C 6H5)2}2Cl2 with acetylenes, olefins, and isothiocyanates
Lee, Chung-L.I.,Hunt, Catherine T.,Balch, Alan L.
, p. 2498 - 2504 (2008/10/08)
Acetylenes with electron-withdrawing substituents react with Pd2(dpm)2X2 (dpm = (C6H5)2PCH2P(C6H 5)2; X = Cl, Br, I) to form Pd2(dpm)2(μ-acetylene)X2 (acetylene = C2(CF3)2, C2(CO2CH3)2, C2(CO2C2H5)2, HC2CO2H, HC2CO2CH3) which have been characterized by infrared and 31P{1H} and 1H NMR spectroscopy. These acetylene adducts are resistant to acetylene exchange and to protonation. Reaction with methyl isocyanide yields [Pd2(dpm)2(μ-C2{CO2CH 3}2)-(CNCH3)2][[PF6] 2 which is also formed by reaction of [Pd2(dpm)2(μ-CNCH3)(CNCH3) 2][PF6]2 with dimethyl acetylenedicarboxylate. Pd2(dpm)2Cl2 is a catalyst for the cyclotrimerization of dimethyl acetylenedicarboxylate and Pd2-(dpm)2(μ-C2{CO2CH 3}2)Cl2 is formed during the reaction. The reaction of Pd2(dpm)2I2 with maleic anhydride results in the formation of Pd(dpm)I2 and two other incompletely characterized products which can also be obtained through the addition of maleic anhydride to Pd2(dpm)3. Ethylene, norbornadiene, and chlorotrifluoroethene are unreactive toward Pd2(dpm)2Cl2. Phenyl and methyl isothiocyanate react with Pd2(dpm)2Cl2 to yield Pd2(dpm)2(μ-CNR)Cl2 in 50% isolated yield; some Pd2(dpm)2(μ-S)Cl2 is formed in the process.
Halogen additions to bis(diphenylphosphino)methane complexes of palladium. Interrelationships of monomeric and dimeric complexes of Pd(II), Pd(I), and Pd(0)
Hunt, Catherine T.,Balch, Alan L.
, p. 2267 - 2270 (2008/10/08)
Addition of halogens (Cl2, Br2, I2) and pentafluorophenyl disulfide to Pd2(dpm)3 (dpm = bis(diphenylphosphino)methane) proceeds stepwise, under stoichiometric control, to yield Pd2(dpm)sub
