Issue 7, 2000
From the journal:

Journal of the Chemical Society, Dalton Transactions

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

Zhaohui Li,a   Zhi-Heng Loh,a   S.-W. Audi Fong,a   Yaw-Kai Yan,b   William Henderson,c   K. F. Moka  and  T. S. Andy Hor*a  

* Corresponding authors

a Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore
E-mail: chmandyh@nus.edu.sg

b Division of Chemistry, National Institute of Education, Nanyang Technological University, 469 Bukit Timah Road, Singapore

c Department of Chemistry, University of Waikato, Private Bag 3105, Hamilton, New Zealand

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.

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Article information

DOI
https://doi.org/10.1039/A909254D
Article type
Paper
Submitted
23 Nov 1999
Accepted
08 Feb 2000
First published
15 Mar 2000

J. Chem. Soc., Dalton Trans., 2000, 1027-1031

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

Z. Li, Z. Loh, S.-W. Audi Fong, Y. Yan, W. Henderson, K. F. Mok and T. S. A. Hor, J. Chem. Soc., Dalton Trans., 2000, 1027 DOI: 10.1039/A909254D

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