Study of ionic and radical reactivities of bridging sulfido ligands in dimeric cyclopentadienyl complexes of molybdenum

Journal Article · Tue Jan 01 04:00:00 EST 1985 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00120a020· OSTI ID:6148501

Casewit, C J; Haltiwanger, R C; Noordik, J; DuBois, M R

Reaction of (CpMo-..mu..-S)/sub 2/S/sub 2/CH/sub 2/ (I, Cp = C/sub 5/H/sub 4/CH/sub 3/) with methyl iodide or methyl fluorosulfate leads to the formation of the cationic dimer ((CpMo)/sub 2/(..mu..-S)(..mu..-SCH/sub 3/)S/sub 2/CH/sub 2/)/sup +/ (II). The bisulfate salt of II has been characterized by an X-ray diffraction study which confirms that a bridging sulfido ligand in I is the site of electrophilic attack. The salt crystallizes in space group P2/sub 1//n with a = 10.155 (2) A, b = 17.478 (9) A, c = 22.201 (7) A, ..beta.. = 97.89 (2)/sup 0/, and V = 3903 (2) A/sup 3/. The electrochemical characteristics of II are compared to those of related molybdenum dimers. II undergoes two reversible one-electron reductions in acetonitrile at -0.34 and -1.24 V vs. SCE to form a neutral mixed valence Mo(III)/Mo(IV) dimer, V, and an anionic Mo(III)/Mo(III) derivative, VII, respectively. The reactivity of each member of this redox series has been characterized. The bridging sulfido ligand in II reacts readily with carbanions and alkyl-substituted borohydride reagents. In contrast, the sulfido ligand in VII is strongly nucleophilic. For example, VII reacts with acetylene to form, upon protonation, the ethenyl thiolate bridged derivative (CpMo)/sub 2/(..mu..-SC/sub 2/H/sub 3/)(..mu..-SCH/sub 3/)S/sub 2/CH/sub 2/ (IV). The reactivity of the unsaturated ligand in IV toward further reduction has been investigated. 38 references, 3 figures, 3 tables.

• Research Organization: Univ. of Colorado, Boulder
• OSTI ID: 6148501
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 4:1; ISSN ORGND
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKENES
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
CYCLOALKENES
CYCLOPENTADIENE
DATA
DIENES
DIMERS
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
MOLYBDENUM COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
ORGANOMETALLIC COMPOUNDS
POLYENES
REDOX REACTIONS
TRANSITION ELEMENT COMPLEXES