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The complex [Re 2 (CO) 8 (MeCN) 2 ] 1 reacted with thiols or H 2 S, respectively, by SH oxidative addition in toluene at 80 ЊC to give hydrido sulfido bridged dirhenium complexes of the general formula [Re 2 (µ-H)(µ-SR)(CO) 8 ] (R = H 2a, n-Bu 2b, Cy 2c, Ph 2d, C 6 H 4 F-p 2e, C 6 F 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 (µ-H)(CO) 8 } 2 (µ 4 S)] 3. In order to demonstrate the acidity of the µ-H ligand 2g was deprotonated by the base 1,8-diazabicyclo[5.4.0]undec-7-ene to give the anion [Re 2 (µ-S(2-naph))(CO) 8 ] Ϫ 4 Ϫ (naph = naphthyl) which can be isolated as its PPh 4 ϩ 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 )(µ-S(2-naph))(CO) 8 ] (M = Au 5a, Ag 5b or Cu 5c) and PPh 4 Cl. The molecular structures of 5a and 5b have been established by single crystal X-ray analysis.

Re 2 (µ-H)(µ-SH)(CO) 8 ] 1 reacted with [Re 2 (CO) 8 (MeCN) 2 ], [Os 3 (CO) 11 (MeCN)], [Co 2 (CO) 8 ] and [Fe 2 (CO) 9 ], respectively, by SH oxidative addition to give the spirocyclic cluster complexes [{Re 2] 5 in good yields. Complexes 2, 3 and 4 have been characterised by crystal structure analysis. Cluster complex 2 consists of two hydrido bridged dirhenium octacarbonyl units linked by a tetrahedral µ 4 -S. The crystal structure of 3 shows an analogous Re 2 unit and a planar Os 3 ring linked by a tetrahedral µ 4 -S. Cluster complex 4 consists of one Fe 2 and two Re 2 units linked into a chain by two tetrahedral µ 4 -S bridges. The structure of 5 is similar to that of 4 and was derived from spectroscopic data and elemental analysis. The formation of 3 was shown to proceed in two steps. First the acetonitrile ligand in [Os 3 (CO) 11 (MeCN)] is substituted by 1 followed by SH oxidative addition giving the intermediate [(OC) 8 (µ-H)Re 2 (µ 3 -S)Os 3 (µ-H)(CO) 11 ] 6. Upon heating the cluster complex eliminates one equivalent of CO yielding 3 as the final product. The molecular structure of 6 has been established by single crystal X-ray analysis.

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