The first report of the reaction of Davy's reagent with [CpMo(CO)(n)](2) (n=2,3) via a phosphorus-sulfur bond cleavage process. Isolation and characterization of CpMo(CO)(2)(S2P(SPhMe)(2)), Cp2Mo2(CO)(5)(S2P(SPhMe)) and Cp2Mo2(mu-S)(mu-S-2)(mu-SPhMe) (Cp = (eta(5)-C5H5))
Document Type
Article
Publication Date
1-1-2010
Abstract
The reaction of [CpMo(CO)(3)](2) (1) and its congener, the triply bonded [CpMo(CO)(2)](2) (2) with 2,4-bis(p-tolylthio) 1,3-dithia-2,4-diphosphetane-2,4-disulfide (DR, Davy's reagent) in toluene at 110 and 70 degrees, respectively, led to the isolation of dark brown solids of CpMo(CO)(2)(S2P(SPhMe)(2)) (3), deep pink solids of Cp2Mo2(CO)(5)(S2P(SPhMe)) (4) and dark purple solids of Cp2Mo2(mu-S)(mu S-2)(mu-SPhMe) (5) with yields dependent on reaction conditions. Thermolytic studies followed by H-1 NMR indicated that 3 and 4 had degraded to 5. The postulated mechanism involves P-S bond cleavage in DR leading to a ring opening and desulfurization process. (C) 2010 Elsevier B. V. All rights reserved.
Keywords
Davy's reagent, Desulfurization, Thermolytic studies, P-S bond cleavage, Ring opening
Publication Title
Inorganica Chimica Acta
Volume
363
Issue
10
Publisher
Elsevier
Publisher Location
PO BOX 564, 1001 LAUSANNE, SWITZERLAND