Structural characterization of [(μ-H)Os3(CO)10(μ-NH2)] and a new polymorphic form of [(μ-H)Os3(CO)10(μ-SH)]. Influence of the bridging group on the geometry of compounds [(μ-H)Os3(CO)10(μ-X)] (X = NH2, NRH, PRH, SbR2, OH, SH, SR, SeR, Cl, Br). R

Compounds [(μ-H)Os3(CO)10(μ-NH2)] and a new polymorphic form of [(μ-H)Os3(CO)10(μ-SH)] were obtained from the reaction of [H2Os3(CO)10] with 1,3,5-N,N,N,-trimethyl-triazinane and 1,3,5-trithiane respectively. The structures show the same geometry described for other doubly bridged triangular clusters. A comparison of these type of compounds show that the bridging group does not affect significantly the dihedral angle between Os3 and Os2X planes (X = NH2, NRH, PRH, SbR2, OH, OR, SH, SR, SeR, Cl and Br). The presence of a hydrogen atom on the bridge could favor a possible interaction between groups so the crystal packing is analyzed. Since intermolecular interactions could also be occurring in solution, reactions of [(μ-H)Os3(CO)10(μ-OH)] and [(μ-H)Os3(CO)10(μ-SH)] with proton sponge were carried out in order to determine if the OH or SH protons had acidic character and could react with a base. These results and other structural characteristics will be discussed.