The syntheses of novel sulfur centred spirocyclic cluster complexes starting from [Re-2(mu-H)(mu-SH)(CO)(8)]

摘要

Re-2(mu -H)(mu -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(mu -H)(CO)(8)}(2)(mu (4)-S)] 2, [(OC)(8)(mu -H)Re-2(mu (4)-S)Os-3(mu -H)(CO)(10)] 3, [(OC)(8)(mu -H)Re-2(mu (4)-S)Fe-2(CO)(6)(mu (4)-S)Re-2(mu -H)(CO)(8)] 4 and [(OC)(8)(mu -H)Re-2(mu (4)-S)Co-2(CO)(6)(mu (4)-S)Re-2(mu -H)(CO)(8)] 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 mu (4)-S. The crystal structure of 3 shows an analogous Re-2 unit and a planar Os-3 ring linked by a tetrahedral mu (4)-S. Cluster complex 4 consists of one Fe-2 and two Re-2 units linked into a chain by two tetrahedral mu (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)(mu -H)Re-2(mu (3)-S)Os-3(mu -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. [References: 35