Studies of the protonation and oxidation of sulfido ligands in dinuclear molybdenum complexes

Journal Article · Thu Feb 01 04:00:00 EST 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00116a015· OSTI ID:7108061

Birnbaum, J; Godziela, G; Maciejewski, M; Tonker, T L; Haltiwanger, R C; DuBois, M K ^[1]

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1. Univ. of Colorado, Boulder (USA)

Synthetic procedures are described for the preparation of cationic derivatives of the formula ((Cp{prime}Mo){sub 2}(S{sub 2}CH{sub 2})({mu}-S) ({mu}-SH)){sup +}, where Cp{prime} = C{sub 5}H{sub 5} (a), C{sub 5}H{sub 4}Me (b), or C{sub 5}Me{sub 5} (c). Spectroscopic data for the protonated complexes are reported, and pK{sub a} values for the {mu}-SH ligands have been determined in acetonitrile. Oxidation of the protonated complexes results in the formation of a dicationic derivative of the formula ((Cp{prime}Mo({mu}-S)){sub 2}S{sub 2}CH{sub 2}){sub 2}{sup 2+}, 2. Both the triflate and tetrafluoroborate salts of 2b have been characterized by X-ray diffraction studies. The triflate salt crystallized in space group C2/c with a = 35.498 (10) {angstrom}, b = 14.823 (7) {angstrom}, c = 17.246 (5) {angstrom}, and {beta} = 115.51 (2){degree}. The tetrafluoroborate salt crystallized in space group P2{sub 1}/n with a = 11.476 (5) {angstrom}, b = 13.843 (6) {angstrom}, c = 12.577 (4) {angstrom}, and {beta} = 112.97 (3){degree}. The structures confirm that two dinuclear units have interacted through formation of a S-S bond between {mu}-sulfido ligands. The reaction of hydrogen (1 atm) with 2 at room temperature resulted in the hydrogenolysis of the intermolecular S-S bond and the formation of 1.

• OSTI ID: 7108061
• Journal Information: Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:2; ISSN 0276-7333; ISSN ORGND
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360102 -- Metals & Alloys-- Structure & Phase Studies
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CALCULATION METHODS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
INFORMATION
LIGANDS
MEASURING INSTRUMENTS
MEASURING METHODS
MOLYBDENUM COMPLEXES
NUMERICAL DATA
SPECTROSCOPY
SULFUR COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES