Synthesis, structure and reactivity of binuclear metal-metal bonded molybdenum(V) and tungsten(V) thioselenohalides: Molecular structure of Mo2(μ-S2)2Cl6(SeCl2)2 and W2(μ-S2)2Cl6(SeCl2)2 View Full Text


Ontology type: schema:ScholarlyArticle     


Article Info

DATE

1997-03

AUTHORS

Vladimir L. Kolesnichenko, Victor B. Rybakov, Leonid A. Aslanov, Sergei V. Volkov

ABSTRACT

Thioselenohalide complexes Mo2(μ-S2)2Cl6(SeCl2)2 (I), Mo2(μ-S2)2Br6(SeBr2)2 (II), and W2(μ-S2)2Br6(SeBr2)2 (III) were synthesized by the reactions of corresponding metal halides or carbonyls or molybdenum metal with excesses of S2X2+Se2X2 mixtures. The complex W2(μ-S2)2Cl6(SeCl2)2 (IV) was obtained by an exchange reaction between (III) and excess of Se2Cl2. Coordination of the neutral SeX2 ligands to thiohalidesM2(μ-S2)2X6 results in higher thermal stability, and suggests the possibility to synthesize SeX2 complexes of the unstable parent tungsten thiohalides. An unusual oxidative addition reaction of (I) was detected: {fx27-1} Both (I) and (IV) were characterized by X-ray crystal structure analysis. They are isostructural and form discrete molecules. Bridging S22− ligands are coordinated perpendicularly to the metal-metal bond;d(M−M)=2.8066 Å and 2.793 Å for I and IV, respectively. Nonequivalence of chlorine atoms which are bound to the metal atom, relate to nonequivalence of halogen atoms in the complexesM2(μ−S2)2X82−. Chlorine atomstrans to SeCl2 ligands form short bonds with the metal; the corresponding35Cl NQR frequency is increased. The selenium dichloride ligand is ambidentate. The selenium atom binds as a donor to the metal and as an acceptor to two chlorine atoms which are also bound covalently to the same metal atom. More... »

PAGES

27-45

References to SciGraph publications

Identifiers

URI

http://scigraph.springernature.com/pub.10.1007/bf02764127

DOI

http://dx.doi.org/10.1007/bf02764127

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