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• W1987818441 endingPage "124" @default.
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• W1987818441 abstract "The mercury(II) phosphine complexes (R3P)2HgX2 (R3P = PPh3, PEt3, 1-phenyldibenzophosphole (DBP), 1-phenyl-3, 4-dimethylphosphole (DMPP); X = Cl, Br, I and PBu3; X = Cl) have been prepared and their solution and solid state structures determined by a combination of elemental analyses, IR, Raman NMR spectroscopy. The structures of (DBP)2HgBr2 (1), (PPh3)2Hg2Br4 (2), (DMPP)2Hg2I4 (3) and (Bu3P)2Hg2I4 (4) have been determined from three-dimensional X-ray data collected by counter methods. Compound 1 crystallizes in space group P1 with a = 10.568(6), b = 17.390(6), c = 9.610(3) Å, α = 106.02(4), β = 100.62(4), γ = 101.41(5)° and Z = 2. Compound 2 crystallizes in space group P21/a with a = 18.619(7), b = 10.938(4), c = 18.762(5) Å, β = 90.36(2)° and Z = 4. Compound 3 crystallizes in space group Pbc21 with a = 8.516(4), b = 19.404(7), c = 19.545(6) Å and Z = 4. Compound 4 crystallizes in space group P21/c with a = 16.450(16), b = 20.609(21), c = 24.263(31) Å, β = 109.38(8)° and Z = 8. Compound 1 deviates from idealC2 symmetry having slightly different HgBr (2.618(2), 2.604(2) Å) and HgP (2.513(3), 2.490(3) Å bond distances. The inequivalence of the phosphines is manifested as a second order ABX CP/MAS 31P{1H} NMR spectrum for 1. Compound 2 is a symmetric doubly bromide bridged dimer with essentially equivalent HgP (2.40(2), 2.44(2) Å) bond distances but its CP/MAS 31P{1H} NMR spectrum displays two AX resonances, showing that the phosphines are not magnetically equivalent. Compound 3 is a symmetric, doubly iodide bridged dimer having slightly different HgP (2.437(7), 2.470(7) Å) bond distances displays three AX resonances in its CP/MAS 31P{1H} NMR spectrum. Compound 4 is an unsymmetrical doubly iodide bridged dimer [(Bu3P)2HgI2HgI2] having equivalent HgP (2.393(21), 2.391(22) Å bond lengths but its CP/MAS 31P{1H} NMR spectrum shows two ABX resonances arising from the two different molecules in the unit cell with the phosphines being magnetically inequivalent in each molecule. Variable temperature 31P NMR spectroscopy shows that equilibria between monomeric (R3P)2HgX2 and dimeric [R3PHgX2]2 occur in solution for R3P = DMPP and Bu3P the dimers are very easily formed from the monomers." @default.
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• W1987818441 date "1993-08-01" @default.
• W1987818441 modified "2023-10-07" @default.
• W1987818441 title "Crystal structures vibrational 31p NMR studies of complexes of tertiary phosphine ligands with mercury(II) halides" @default.
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• W1987818441 doi "https://doi.org/10.1016/s0020-1693(00)82830-3" @default.
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