Item

Ligand-stabilization of an unusual square-based pyramidal geometry of Cd(II) and Zn(II) in an heterometallic {MPt₂S₂} core (M = Cd, Zn)

Abstract
Two heterometallic complexes, [Pt₂MCl(bipy)(PPh₃)₄(μ₃-S)₂][PF₆] (M = Zn, 2, Cd, 3) were synthesized from [Pt₂(PPh₃)₄(μ-S)₂] and characterized by single-crystal X-ray diffraction and electrospray ionization mass spectrometry. Two unusual square-based pyramidal (sbp) Zn(II) and Cd(II) structures are evident. VT 31P-{1H} NMR studies showed that 2 and 3 are fluxional at rt whereby rapid ligand exchange takes place by a non-dissociative mechanism. At intermediate temperatures, this motion slows down to a flipping movement of the {Pt₂S₂} ligand. At 183 K, all four phosphines are inequivalent in a distorted sbp model similar to that observed in the solid state. Nonlocal density functional theory calculations reveal that the formation of a trigonal bipyramidal intermediate in the fluxional process is favored over that of the tetrahedral species for both 2 and 3. The M–Cl (M = Zn, Cd) bonds are notably strong.
Type
Journal Article
Type of thesis
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Citation
Li, Z., Loh, Z. –H., Fong, S. W. A., Yan, Y. –K., Henderson, W., Mok, K. F., & Hor, T. S. Andy. (2000). Ligand-stabilization of an unusual square-based pyramidal geometry of Cd(II) and Zn(II) in an heterometallic {MPt₂S₂} core (M = Cd, Zn). Journal of Chemical Society Dalton Transactions, 1027-1031.
Date
2000
Publisher
ROYAL SOC CHEMISTRY
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