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Title: Ligand-stabilization of an unusual square-based pyramidal geometry of Cd(n) and Zn(n) in an heterometallic {MPt2S2} core (M = Cd, Zn)
Authors: Li, Z.
Loh, Z.-H.
Audi Fong, S.-W.
Van Yaw-Kai
Henderson, W.
Mok, K.F.
Andy Hor, T.S. 
Issue Date: 2000
Citation: Li, Z., Loh, Z.-H., Audi Fong, S.-W., Van Yaw-Kai, Henderson, W., Mok, K.F., Andy Hor, T.S. (2000). Ligand-stabilization of an unusual square-based pyramidal geometry of Cd(n) and Zn(n) in an heterometallic {MPt2S2} core (M = Cd, Zn). Journal of the Chemical Society, Dalton Transactions (7) : 1027-1031. ScholarBank@NUS Repository.
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 spcctrometry. Two unusual square-based pyramidal (sbp) Zn(n) and Cd(n) 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-C1 (M = Zn, Cd) bonds are notably strong. © The Royal Society of Chemistry 2000.
Source Title: Journal of the Chemical Society, Dalton Transactions
ISSN: 1470479X
DOI: 10.1039/a909254d
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