Specific features of the structure of tungsten(VI) mononuclear six-coordinate oxohalide complexes: A review
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CTURE OF INORGANIC COMPOUNDS Dedicated to the memory of G.B. Bokiі on the occasion of his 100th birthday
Specific Features of the Structure of Tungsten(VI) Mononuclear SixCoordinate Oxohalide Complexes: A Review V. S. Sergienkoa,*, V. L. Abramenkob, and A. V. Churakova a
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskiі pr. 31, Moscow, 119991 Russia * email: [email protected] b EastUkrainian Volodymyr Dahl National University, kv. Molodyozhny 20a, Luhansk, 91034 Ukraine Received February 11, 2009
Abstract—The specific features revealed in the structure of the mononuclear octahedral oxohalide com plexes of tungsten(VI) have been considered. The structural features of tungsten(VI) monooxo and dioxo complexes, as well as pseudodioxo compounds (tungsten(VI) monoxo complexes containing an additional multiply bonded ligand (=Y) of another type), have been analyzed. PACS numbers: 61.66.Fn DOI: 10.1134/S1063774509050095
CONTENTS 1. Introduction 2. Structure of the Monomeric SixCoordinate Monooxohalide Complexes of Tungsten(VI) 3. Structure of the Monomeric SixCoordinate Monooxohalide Complexes of Tungsten(VI) with the Second Multiply Bonded Ligand 4. Structure of the Monomeric Octahedral Dioxo halide Complexes of Tungsten(VI) 5. A Comparison of the Geometric Parameters of the Monomeric Octahedral Monooxohalide and Dioxohalide Complexes of Tungsten(VI) 6. Conclusions References 1. INTRODUCTION In this review paper, we consider the specific fea tures revealed in the structure of monomeric sixcoor dinate oxohalide complexes of tungsten(VI) with mul 1
tiple bonds M=O. Before proceeding to the systematic presentation of the material, we note two general features of the structure of oxo complexes of Group V–VII d0 metals, including hexavalent tungsten. 1
With a few exceptions, structures with a disordered (statistical) arrangement of ligands, in particular, the O(oxo) and halogen atoms, in tungsten(VI) oxohalide complexes are not considered in the present review.
(1) The mutual arrangement of multiply bonded oxo ligands in octahedral dioxo complexes is deter mined by the electronic configuration of the metal: the complexes of d0 metals are characterized by the cis arrangement [1, 2], which provides the maximum par ticipation of all three t2g orbitals (dxy, dxz, dyz) in the π acceptance of electrons of the O(oxo) ligands. (2) The choice of the trans partner from a set of competing functional groups is determined by the so called “selfconsistency rule” [3, 4]. According to this rule, the trans position with respect to the multiply bonded ligand is predominantly occupied by the least polarizable σ donor, the bond to which can be weak ened more easily (in particular, the neutral ligand is preferable to the acido ligand). The structural manifestation of the trans effect of a multiple bond can be quantitatively characterized by the parameter ∆, which is the difference between the lengths of the bonds of the metal with the trans partner and a sim ilar ligand in the c
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