@article {339,
	title = {Crystallographic characterization of the palladium(I) dimers, syn-Pd2Cl2(dppmMe)(2) and Pd2Cl2(dpPM)(2); solution conformational behavior of syn- and anti-Pd2Cl2(dppmMe)(2) and their (mu-Se) adducts [dppmMe = mu-1,1-bis(diphenylphosphino)ethane, and dppm},
	journal = {Inorganica Chimica Acta},
	volume = {327},
	year = {2002},
	note = {ISI Document Delivery No.: 509WATimes Cited: 16Cited Reference Count: 51},
	month = {Jan},
	pages = {179-187},
	type = {Article},
	abstract = {An X-ray diffraction study on syn-Pd2Cl2(dppmMe)(2), syn-1, shows an unusual boat-like conformation of the eight-membered Pd2P4C2 ring. This conformation, containing equatorial Me groups, facilitates access of the Pd-Pd bond to small molecules such as CO, SO2, and elemental sulfur or selenium, and makes the syn isomer more reactive than anti-1. A comparison of bond angles around the Pd and P atoms in the syn- and anti-isomers reveals a more strained geometry of the former, which may also contribute to the stronger propensity of syn-1 to form A-frame adducts. Solution NMR/NOE studies on syn- and anti-1 and their (mu-Se) adducts reveal the structural rigidity of these complexes; the Me groups inhibit the interchange of axial and equatorial positions on the bridging methine C-atom, and solution structures correspond to those in the solid state. The X-ray structure of Pd2Cl2(dppm)(2) is, as expected, like that of the corresponding bromo, complex; both are analogous to that of anti-1 which adopts a chair conformation within both the fused, five-membered rings. (C) 2002 Elsevier Science B.V.. All rights reserved.},
	keywords = {1, 1-bis(diphenylphosphino)ethane, Aa-frame complexes, bis(diphenylphosphino)methane, BIS(DIPHENYLPHOSPHINO)METHANE LIGANDS, BRIDGING, CARBON-MONOXIDE, COMPLEXES, DINUCLEAR PALLADIUM(I), METAL-METAL BONDS, MOLECULAR-STRUCTURE, palladium complexes, PLATINUM(I), RAY CRYSTAL-STRUCTURES, SELENIDE, selenium compounds},
	isbn = {0020-1693},
	url = {<Go to ISI>://000173171700020},
	author = {Besenyei, G. and Parkanyi, L. and Gacs-Baitz, E. and James, Brian R.}
}
@article {3566,
	title = {{KINETIC AND MECHANISTIC ASPECTS OF SULFUR ABSTRACTION FROM PD(2)X(2)(MU-S)(MU-DPM)(2) USING DPM OR DPMME [X=HALIDE},
	journal = {Inorganic Chemistry},
	volume = {34},
	number = {9},
	year = {1995},
	note = {ISI Document Delivery No.: QV824Times Cited: 23Cited Reference Count: 30},
	month = {Apr},
	pages = {2278-2286},
	type = {Article},
	abstract = {Solution kinetic and mechanistic studies were performed on the abstraction of sulfur from Pd(2)X(2)(mu-S)(mu-dpm)(2) [X = Cl (2a), Br (2b), I(2c)] using bis(diphenylphosphino)methane (dpm) to give, respectively, Pd(2)X(2)(dpm)(2) [X = Cl (1a), Br (1b), I (1c)] and dpm(S). The reaction is first-order in both 2 and dpm with the reactivity trend in CHCl3 being X = Cl > Br > I. The activation parameters for the chloride system are Delta H-double dagger = 41 +/- 3 kJ mol(-1) and Delta S-double dagger = -127 +/- 10 J K-1 mol(-1), and for the bromide, Delta H-double dagger = 38 +/- 1 kJ mol(-1) and Delta S-double dagger = -144 +/- 4 J K-1 mol(-1), showing the entropy term is dominant in governing reactivity. Low-temperature NMR studies did not reveal the presence of observable intermediates. 2b and 1b undergo rapid diphosphine ligand exchange with dpm-d(2); with 2b, prior to any S-abstraction, Pd2Br2(mu-S)(dpm)(dpm-d(2)) (7b) and Pd2Br2(mu-S)(dpm-d(2))(2) (8b) are present, while Pd2Br2(dpm)(dpm-d(2)) (3b) and Pd2Br2(dpm-d(2))(2) (4b) are formed, as well as 1b and dpm(S)-d(2), in the abstraction reaction of 2b with dpm-d(2). The distribution of products is close to statistical on the basis of the stoichiometries of the reactants. Reaction of 2b with 1,1{\textquoteright}-bis(diphenylphosphino)ethane (dpmMe) proceeds in an analogous way generating 1b, Pd2Br2(dpm)(dpmMe) (5b), Pd2Br2(dpmMe)(2) (6b), dpm(S), and dpmMe(S). In contrast, 1b undergoes slow diphosphine ligand exchange with dpmMe to form 5b and 6b; 2b undergoes no ligand exchange with dpmMe prior to the S-abstraction reaction. The findings are rationalized in terms of postulated intermediates and transition states that include formulations with three equivalent diphosphines. No sulfur abstraction occurs on treating 2b with PPh(3), PPh(2)Me, or Ph(2)P(CH2)(3)PPh(2).},
	keywords = {BIS(DIPHENYLPHOSPHINO)METHANE DPM, BIS-PHOSPHORUS LIGANDS, COMPLEXES, CRYSTAL-STRUCTURE, DERIVATIVES, DINUCLEAR PALLADIUM(I), HYDROGEN-SULFIDE, METAL-METAL BONDS, MONONUCLEAR, Pd(I)},
	isbn = {0020-1669},
	url = {<Go to ISI>://A1995QV82400007},
	author = {Wong, T. Y. H. and Barnabas, A. F. and Sallin, D. and James, Brian R.}
}
