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Oxidation and acidolysis of MoH/sub 4/(PR/sub 3/)/sub 4/

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00142a015· OSTI ID:6540218
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MoH/sub 4/(PMe/sub 2/Ph)/sub 4/ reacts with 2 mol of AgBF/sub 4/ in MeCN to give (MoH/sub 2/(PMe/sub 2/Ph)/sub 4/(NCMe)/sub 2/)(BF/sub 4/)/sub 2/, characterized by spectroscopic methods and x-ray crystallography as containing a fluxional dodecahedral dication. Reaction with equimolar AgBF/sub 4/ gives no new product but only a reduced yield of the same salt. This oxidation is thus followed by reductive elimination of H/sub 2/ so that the molybdenum oxidation state suffers no net change. The same salt is obtained by treating the tetrahydride with 2 mol of HBF/sub 4/.OEt/sub 2/ in acetonitrile. The identity of the phosphine affects the product isolated: MoH/sub 2/(PMePh/sub 2/)/sub 4/, upon treatment with AgBF/sub 4/ or HBF/sub 4/.OEt/sub 2/ in MeCN, yields MoH/sub 2/(PMePh/sub 2/)/sub 3/(NCMe)/sub 3//sup 2 +/ with liberation of 1 mol of PMePh/sub 2/. Possible mechanisms are discussed, as is the relationship between silver oxidation and acidolysis. Crystallographic data (at -160/sup 0/C) for (MoH/sub 2/(PMe/sub 2/Ph)/sub 4/(NCMe)/sub 2/)(BF/sub 4/)/sub 2/: monoclinic space group P2/sub 1/ with a = 12.359 (6) A, b = 33.323 (2) A, c = 13.048 (6) A, ..beta.. = 128.61 (2)/sup 0/, Z = 4. R(F) = 0.0673 for 5037 data collected by diffractometer. 3 figures, 4 tables.

Research Organization:
Indiana Univ., Bloomington
OSTI ID:
6540218
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 21:12; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BORON COMPOUNDS
BORON FLUORIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
KINETICS
LATTICE PARAMETERS
MOLYBDENUM COMPLEXES
MONOCLINIC LATTICES
OXIDATION
PHOSPHINES
PHOSPHORUS COMPOUNDS
REACTION KINETICS
SILVER COMPOUNDS
SILVER FLUORIDES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS