Coordination Chemistry Reviews 213 (2001) 51 – 77

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The characteristic IR spectra of heterothiometallic cluster compounds

Chi Zhang a, Guo-Cheng Jin a, Jin-Xi Chen a,

Xin-Quan Xin a,*, Ke-Ping Qian b

a State Key Laboratory of Coordination Chemistry, Department of Chemistry, Nanjing Uniuersity,

Nanjing 210093, PR China

b Department of Physiology, Uniuersity of Florida, Miami, FL 100274, USA

Received 3 January 2000; received in revised form 14 April 2000; accepted 5 June 2000

Contents

Abstract 52

1. Introduction 52
2. General study 52
3. Classification and explanation 58
   1. The clusters containing one M atom and no O atom 59
   2. The clusters containing one M atom and one O atom 60
   3. The clusters containing di- or poly-M atoms 66
      1. Trinuclear clusters (two M atoms and one M atom) 66
      2. Hexanuclear clusters 66
      3. Heptanuclear clusters (two M atoms and five M atoms) 68
      4. Octanuclear clusters 68
      5. Dodecanuclear clusters (four M atoms and eight M atoms) 69
      6. Tetradecanuclear clusters (four M atoms and ten M atoms) 69
      7. Eicosanuclear clusters (eight M atoms and 12 M atoms) 70
4. Discussion 71
   1. Different coordination environments of sulfur atoms 72
   2. Different d-electron configuration 72
   3. Influence of periphery ligands 72
   4. Coupling vibrations 73
5. Conclusions 73

Acknowledgements 74

References 74

* Corresponding author. Tel.: 86-25-3593132; fax: 86-25-3314502.

E-mail address: xxin@netra.nju.edu.cn (X.-Q. Xin).

0010-8545/01/$ - see front matter copy; 2001 Elsevier Science B.V. All rights reserved. PII: S0010-8545(00)00377-5

52 C. Zhang et al. / Coordination Chemistry Reuiews 213 (2001) 51 – 77

Abstract

This article summarizes and presents the obtainable characteristic IR spectra of the existing heterothiometallic cluster compounds containing the [MXS₃]2 minus; (X=O, S; M=V, Mo, W, Re) moiety. The M–S stretching vibration modes are classified into four categories including r(M–S_t), r(M–micro;₂-S), r(M–micro;₃-S) and r(M–micro;₄-S) according to the different conjunc- tion ways between the transition metal and sulfur atoms. The structures of the heteroth- iometallic cluster compounds could be inferred from their characteristic IR spectra, the core structurersquo;s symmetry of the heterothiometallic clusters and the M/M ratio. copy; 2001 Elsevier Science B.V. All rights reserved.

Keywords: Characteristic IR spectra; Heterothiometallic cluster compounds

Introduction

Heterothiometallic cluster chemistry is one of the most important and active areas in inorganic and physical chemistry [1 – 6] because it plays a special role in catalysis reactions [7 – 10], biological processes [11 – 13] and advanced materials [14 – 16]. During the past two decades, over 300 heterothiometallic cluster com- pounds containing the [MXS₃]2 minus; (X=O, S; M=V, Mo, W, Re) moiety have been synthesized and studied extensively [17 – 19]. However, the IR spectra of the heterothiometallic clusters have not been studied and summarized systematically. The relationship between the IR spectra of the heterothiometallic clusters and their structures has not been investigated thoroughly. The IR spectra of heterothiometal- lic cluster compounds as well as their UV– vis spectra, Elemental analyses and Raman spectra are usually regarded as supplemental proofs of the crystal structures determined by X-ray diffraction. In this article, the characteristic IR spectra of the heterothiometallic clusters with the [MXS₃]2 minus; moiety are studied and summarized systematically. The structures of the heterothiometallic clusters could be inferred by studying and analyzing their characteristic IR spectra, the core structurersquo;s symme- try, and the M/M ratio.

General study

The low wave-number region of the IR spectra of heterothiometallic cluster compounds containing the [MXS₃]2 minus; (X=O, S; M=V, Mo, W, Re) moiety has proven valuable in arguments concerning their electronic and structural characteris- tics [1b,17,19]. The [MXS₃]2 minus; moiety as a bidentate ligand always coordinates with M (M=Cu, Ag, Au, Pd, Pt, Zn, Cd, Hg, Fe, Co, Ni, Sn, Ru) in the pattern of , while according to our knowledge, only one example (Table 1, no. 95) with another conjunct pattern M–S–M, has been found.

The molecular spherical space arrangement of every heterothiometallic cluster compound containing the [MXS₃]2 minus; moiety may be divided into three spheres. There are four or three sulfur atoms and one oxygen atom in the first sphere. The

Table 1

IR spectral parameters of the first category of the heterothiometallic cluster compounds

Number

Compound

M–S_t M–micro;₂-S M–micro;₃-S M–micro;₄-S M-micro;_c-S Symmetry group of core Ref.

C. Zhang et al. / Coordination Chemistry Reuiews 213 (2001) 51 – 77

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