Structural dependencies of pyramidal inversion at sulphur and selenium in thio- and seleno- ether complexes of palladium(II) and platinum(II): A nuclear magnetic resonance study |
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Authors: | EW Abel SK Bhargava K Kite KG Orrell V Šik BL Williams |
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Institution: | Department of Chemistry, The University, Exeter EX4 4QD, England |
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Abstract: | Total NMR band shape fitting methods have provided accurate energy data for inversion barriers at sulphur and selenium in complexes of types cis-MX2L] (M = PdII, PtII; X = Cl, Br, I; L = MeS(CH2)2SMe, MeS(CH2)3SMe, o-(SMe)2C6H3Me, cis-MeSCH=CHSMe) and PtXMe{MeE(CH2)2E′Me}] (E= E′= S or Se and E = S, E′= Se; X = Cl, Br, I). Barrier energies were found to decrease by 10–12 kJ mol?1 in going from aliphatic through aromatic to olefinic ligand back-bone. This can be explained in terms of (3p - 2p) π conjugation between the inverting centre and the ligand back-bone. The effects of ligand ring size, nature of halogen atom and the metal oxidation state on the barrier energies are discussed. |
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Keywords: | Author to whom correspondence should be addressed |
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