摘要
The reaction of [Ru3(CO)10(脦脦-dppm)] (1) with dppmSe at 66 脦脦C affords [Ru3(CO)8(脦脦-dppm)2] (2), [Ru3(CO)7(脦脦3-CO)(脦脦3-Se)(脦脦-dppm)] (3), [Ru3(CO)5(脦脦3-CO)(脦脦3-Se)(脦脦-dppm)2] (4) and [Ru3(CO)6(脦脦3-CO)(脦脦3-Se)(脦脦-dppm)(脦脦1-Ph2PCH2P(O)Ph2)] (5) in 7%, 5%, 9%and 33%yields, respectively. A similar reaction between 1 with dppmS gives [Ru3(CO)7(脦脦3-S)2(脦脦-dppm)] (6), [Ru3(CO)7(脦脦3-CO)(脦脦3-S)(脦脦-dppm)] (7) [Ru3(CO)5(脦脦3-CO)(脦脦3-S)(脦脦-dppm)2] (8) and [Ru3(CO)6(脦脦3-CO)(脦脦3-S)(脦脦-dppm)(脦脦1-Ph2PCH2P(O)Ph2)] (9) in 8%, 7%, 14%and 35%yields, respectively. Treatment of 1 with PhSeSePh at 66 脦脦C affords the dinuclear compound [Ru2(CO)4(脦脦-SePh)2(脦脦-dppm)] (10) in 14%yield. Thermolysis of 5 and 9in refluxing toluene at 110 脦脦C gives 4 and 8, respectively. The molecular structures of 4, 9 and 10 have been determined by single-crystal X-ray diffraction studies. The cores of the new clusters 4, 5, 8 and 9 consist of metal triangles capped by 脦脦3-sulfur or selenium atoms with the bidentate ligand bridging in equatorial positions. In compounds 4 and 8, two bidentate dppm ligands bridge the Ru3 triangle in such a way that each ligand bridges two ruthenium atoms and one Ru脦脦脦Ru edge remains unbridged. Compounds 5 and 9 contain one bridging dppm ligand and one dangling dppm mono-oxide ligand Ph2PCH2P(O)Ph2 coordinated to the rear metal atom at an equatorial position. The molecular structure of 10 shows classical 脦脦脦sawhorse脦脦脦 structure with two bridging SePh ligands as well as the dppm ligand.