Activation of hydrogen by cationic cyclopentadienyl molybdenum dimers with sulfido ligands. 4. A cationic complex with an allyl thiolate ligand

Journal Article · Thu Dec 01 04:00:00 EST 1988 · J. Coord. Chem.; (United States)

DOI:https://doi.org/10.1080/00958972.1988.9728142· OSTI ID:5914304

Weberg, R T; Laurie, J C.V.; Rakowski Dubois, M

A mixture of cis,trans-1-bromo-2-butene was reacted with (CpMoS)/sub 2/S/sub 2/CH/sub 2/ (Cp=C/sub 5/H/sub 5/) to form the cationic sulfur-alkylated product ((CpMo)/sub 2/(S/sub 2/CH/sub 2/)(/mu/-S)(/mu/-SCH/sub 2/CH=C(H)Me))Br, (1), which was characterized by spectroscopic methods. The reactivity of the allyl thiolate complex was compared with that of ((CpMo)/sub 2/(S/sub 2/CH/sub 2/)(/mu/-S)(/mu/-SCMe=CHMe))Br, (2) an isomer with a vinyl thiolate ligand. Complex 1 does not undergo detectable isomerization in chloroform solution while a complex rearrangement process was observed for 2. The reaction of 1-2 atm of hydrogen with 1 resulted in the formation of 2-bromobutane and a previously characterized molybdenum complex (CpMoS/sub 2/CH/sub 2/)/sub 2/. ((CpMo)/sub 2/(S/sub 2/CH/sub 2/)(/mu/-S)(/mu/-SCHMe(Et)))Br was an intermediate in this reaction with hydrogen. It was detected by NMR and synthesized by an independent route. The reaction of methyl lithium with 1 led to the formation of a neutral complex (CpMo)/sub 2/(S/sub 2/CH/sub 2/)(/mu/-SME)(/mu/-SCH/sub 2/CH=CHMe), (3). Complex 3 reacted under 1-2 atm of hydrogen to form an isomeric mixture of butenes. The nature of the molybdenum products which were isolated from this reaction suggested that homolytic cleavage of the carbon sulfur bond in the allyl thiolate ligand had occurred. Possible reaction pathways for the transformations of 1 and 3 under hydrogen are discussed.

• Research Organization: Univ. of Colorado, Boulder (USA)
• OSTI ID: 5914304
• Journal Information: J. Coord. Chem.; (United States), Journal Name: J. Coord. Chem.; (United States) Vol. 19:1-3; ISSN JCCMB
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CATIONS
CHALCOGENIDES
CHARGED PARTICLES
CHEMICAL PREPARATION
COMPLEXES
DATA
DIMERS
ELEMENTS
EXPERIMENTAL DATA
HYDROGEN
INFORMATION
IONS
LIGANDS
MOLYBDENUM COMPLEXES
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
SPECTROSCOPY
SULFIDES
SULFUR COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES