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Trans Influence of the Oxo Ligand in the Dimeric Molybdenum(V) Complexes. Crystal Structure Determinations of Caesium Di-μ-oxo-bis[aquaoxalatooxomolybdate(V)] Monohydrate (A) and Potassium Tricaesium Bis{di-μ-sulphido-bis[aquaoxalatooxomolybdate(V)]} Tetrahydrate (B), and Redetermination of the Crystal Structure of Barium Di-μ-oxo-bisLaquaoxalatooxomolybdate(V)] Trihydrate (C) and Pyridinium Di-μ-oxo-bis-[oxotris(isothiocyanato)molybdate(V)] Monohydrate (D)

Boris Kamenar ; Laboratory of General and Inorganic Chemistry, Chemistry Department, Faculty of Science, University of Zagreb, P.O. Box 153, 41001 Zagreb, Croatia
Branko Kaitner ; Laboratory of General and Inorganic Chemistry, Chemistry Department, Faculty of Science, University of Zagreb, P.O. Box 153, 41001 Zagreb, Croatia
Neven Strukan ; Laboratory of General and Inorganic Chemistry, Chemistry Department, Faculty of Science, University of Zagreb, P.O. Box 153, 41001 Zagreb, Croatia

Sažetak

The crystal structures of the title complexes (A) and (B) have been determined and those of (C) and (D) redetermined in order to obtain new and more accurate data for explanation of the trans influence of the terminal oxo- oxygen atom in the di-/c-oxo and di-/c-sulphido molybdenum(V) complexes with oxalato and isothiocyanato ligands. The interatomic distances are discussed and the results compared with similar dimeric structures with molyb- denumCV) in distorted octahedral coordination. Whereas a considerable lengthening of the bonds trans to the multiple-bonded terminal oxo-ligand was found in all structures with a double bridge of oxygen atoms and, therefore, this influence confirmed as a generally valid rule, no such trans influence was observed in the structures with a double bridge of sulphur atoms. In the structures of di-^-sulphido-oxalato complexes, the Mo-L bonds cis to the terminal oxo ligand (i.e. trans to the bridging sulphur atoms) are longer them the bonds in trans position. These results indicate that the sulphur atom has a greater trans influence than the oxygen atom. This effect is not so conspicuous in the isothiocyanato complexes.

Ključne riječi

Hrčak ID:

137303

URI

https://hrcak.srce.hr/137303

Datum izdavanja:

31.12.1991.

Posjeta: 981 *