The reaction of (Re_2(CO)_8(MeCN)_2) with thiols. Formation of hydrido sulfido bridged dirhenium cluster complexes (Re_2(#mu#-H)(#mu#-SR)(CO)_8) (R = H, n-Bu, Cy, Ph, C_6H_4F-p, C_6F_5 or 2-naphthyl)

摘要

The complex [Re_2(CO)_8(MeCN)_2] 1 reacted with thiols or H_2S, respectively, by SH oxidative addition in toluene at 80 deg C to give hydrido sulfido bridged dirhenium complexes of the general formula [Re_2(#mu#-H)(#mu#-SR)(CO)_8] (R = H 2a, n-Bu 2b, Cy 2c, Ph 2d, C_6H_4F-p 2e, C_6F_5 2f or 2-naphthyl 2g) in 60 to 80% yield. Complexes 2c and 2g have been characterised by crystal structure analysis. Complex 2a undergoes reaction with another equivalent of 1 to form the novel spirocyclic complex [{Re_2(#mu#-H)(CO)_8}_2(#mu#_4S)] 3. In order to demonstrate the acidity of the #mu#-H ligand 2g was deprotonated by the base 1, 8-diazabicyclo[5. 4. 0]undec-7-ene to give the anion [Re_2(#mu#-S(2-naph))(CO)_8]~- 4~- (naph = naphthyl) which can be isotated as its PPh_4~+ salt. This reacts with one equivalent of [MCl(PPh_3)](M = Au, Ag or Cu) to give the novel heteronuclear cluster complexes [Re_2(MPPh_3)(#mu#-S(2-naph))(CO)_8] (M = Au 5a, Ag 5b or Cu 5c) and PPh_4Cl. The molecular structures of 5a and 5b have been established by single crystal X-ray analysis.