93111-44-5Relevant academic research and scientific papers
A study of ionic and radical reactivities of bridging sulfido ligands in dimeric cyclopentadienyl complexes of molybdenum
Casewit,Haltiwanger,Noordik,DuBois, M. Rakowski
, p. 119 - 129 (1985)
Reaction of (CpMo-μ-S)2S2CH2 (I, Cp = C5H4CH3) with methyl iodide or methyl fluorosulfate leads to the formation of the cationic dimer [(CpMo)2(μ-S)(μ-SCH3)S2CH 2]+ (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 P21/n with a = 10.155 (2) A?, b = 17.478 (9) A?, c = 22.201 (7) A?, β = 97.89 (2)°, and V = 3903 (2) A?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)2(μ-SC2H3)(μ-SCH3)S 2CH2 (IV). The reactivity of the unsaturated ligand in IV toward further reduction has been investigated.
