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Crystal structures vibrational 31p NMR studies of complexes of tertiary phosphine ligands with mercury(II) halides
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Bowmaker, Graham A., Clase, Howard J., Alcock, Nathaniel W., Kessler, Janet M., Nelson, John H. and Frye, James S. (1993) Crystal structures vibrational 31p NMR studies of complexes of tertiary phosphine ligands with mercury(II) halides. Inorganica Chimica Acta, 210 (1). pp. 107-124. doi:10.1016/S0020-1693(00)82830-3 ISSN 00201693.
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Official URL: http://dx.doi.org/10.1016/S0020-1693(00)82830-3
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 and 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 P1BAR with a = 10.568(6), b = 17.390(6), c = 9.610(3) angstrom, alpha = 106.02(4), beta = 100.62(4), gamma = 101.41(5)-degrees and Z = 2. Compound 2 crystallizes in space group P2(1)/a with a = 18.619(7), b = 10.938(4), c = 18.762(5) angstrom, beta = 90.36(2)-degrees and Z = 4. Compound 3 crystallizes in space group Pbc2(1) with a = 8.516(4), b = 19.404(7), c = 19.545(6) angstrom and Z = 4. Compound 4 crystallizes in space group P2(1)/c with a = 16.450(16), b = 20.609(21), c = 24.263(31) angstrom, beta = 109.38(8)-degrees and Z = 8. Compound 1 deviates from ideal C2 symmetry having slightly different Hg-Br (2.618(2), 2.604(2) angstrom) and Hg-P (2.513(3), 2.490(3) angstrom) bond distances. The inequivalence of the phosphines is manifested as a second order ABX CP/MAS P-31{H-1} NMR spectrum for 1. Compound 2 is a symmetric doubly bromide bridged dimer with essentially equivalent Hg-P (2.40(2), 2.44(2) angstrom) bond distances but its Cp/MAS P-31{H-1} 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) angstrom) bond distances and displays three AX resonances in its CP/MAS P-31{H-1} NMR spectrum. Compound 4 is an unsymmetrical doubly iodide bridged dimer [(Bu3P)2HgI2HgI2] having equivalent Hg-P (2.393(21), 2.391(22) A) bond lengths but its CP/MAS P-31{H-1} 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 P-31 NMR spectroscopy shows that equilibria between monomeric (R3P)2HgX2 and dimeric [R3PHgX2]2 occur in solution and for R3P = DMPP and BU3P the dimers are very easily formed from the monomers.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||
Journal or Publication Title: | Inorganica Chimica Acta | ||||
Publisher: | Elsevier BV | ||||
ISSN: | 00201693 | ||||
Official Date: | 1993 | ||||
Dates: |
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Volume: | 210 | ||||
Number: | 1 | ||||
Number of Pages: | 18 | ||||
Page Range: | pp. 107-124 | ||||
DOI: | 10.1016/S0020-1693(00)82830-3 | ||||
Status: | Peer Reviewed | ||||
Publication Status: | Published | ||||
Access rights to Published version: | Restricted or Subscription Access |
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