Organometallic heterocubane clusters with Co-O and Co-S framework

The reaction of [{(eta(5)-Me5C5)Co}(2)(mu-eta(6):eta(6)-toluene)] with water under different conditions leads to formation of the clusters [{(eta(5)-Me5C5)Co}(3)(mu(3)-O)(2)] (1), [{(eta(5)-Me5C5)Co}(4)(mu(3)-OH)(4)] (2) and [{(eta(5)-Me5C5)Co}(3)(mu(3)-OH)(4)](2)Co (3), whereas its reaction with hydrogen sulfide leads to [{(eta(5)-Me5C5)Co}(3)(mu(3)-S)(4)]Co(mu(3)-S)(2)[(eta(5)-Me5C5)Co](2) center dot Et2O (4). 1, 2 and 4 were characterized by single crystal X-ray diffraction. 1 is composed of a central Co3O2 unit, with two O2- units in an apical postion. The three cobalt atoms form a regular triangle with Co-Co distances of 2.438(2) angstrom, and the two oxygen atoms are located in apical positions of the triangular arrangement. The pentamethylcyclopentadienyl (Cp*) ligands are terminally bonded to the Co atoms in a eta(5)-fashion. The Co and O atoms of 2 form a cubane-type Co4O4 cluster, with eta(5)-bonded Cp* ligands. The central unit of 3 consists of a Co7O8 double cubane framework. Two Co4O4 cluster sharing a common corner (Co atom). Each of the other six Co atoms of the double cubane bound terminally a Cp* ligand. 4 is composed of a [{(eta(5)-Me5C5)Co }(2)(mu(3)-S)(4)](mu(3)-S)(2)[(eta(5)-Me5C5)Co](2) and an ether molecule. 4 contains a central Co4S4 cubane-like unit. One of the four Co atoms is bonded via two mu(3)-S atoms to two additional (eta(5)-Cp*Co) units. The other three Co atoms are eta(5)-coordinated to a Cp* ligand.