2010302010178 ; 化學系 ; Condensation of be triosmium acetonitrile complex Os3(CO)10(NCMe)2 with the sulfido complex CpW(CO)3(CH2SMe) in refluxing THF solution produced three sulfur-containing compounds Os3(C0)10)(µ-H)(µ-SMe) (1), Os3(CO)11 [S(Me)CH2W(CO)3Cp] (2) and CpWOs3(CO)12(µ-CH2)(µ-SMe) (3). Clusters 2 and 3 were products involving a 1:1 combination of starting materials and were characterized by X-ray diffraction studies. Crystals of 2 belongs to monoclinic space group P 21 /c witha=8.418(2),b = 11.912(2),c = 28.288 Å,=97.64(2)°,Z=4;R F=0.044,R W,=0.044. Crystal dara far 3: space group P 21/e,a 18.156(4).b=9.255(6),c = 15.347(4) Å. = 103.49(2)°,Z = 4;R F -=0.047,R W = 0.045. Upon thermolysis in toluene, the methylene cluster 3 released CO and induced C-H bond activation to afford two tetrametallic carbido clusters with formula CPWOS3(CO)9(µ4-C)(µ-H)2(µ-SMe) (4) and CPWOs3(CO)11(µ4-C)(µ-SMe) (5) as the principle products. The first complex possesses a butterfly framework encapsulating a µ4-C ligmd and a µ-SMe ligand linking a W-Os edge, whereas the second product adopts a puckered, cyclic arrangement of WOs3 metal atoms with µ-SMe ligand located on a nonbonding Os-Os vector. Complex4 crystallizes in monoclinic space group P 21 /c witha=15.633(4) Å,b = 8.699 (3) Å,c=15.422(4) Å,=93.12(2)=°, Z=4,R=0.036,R W =0.034 for 2780 observed reflections. Crystal data for5: space groupP nma,a=14.542(3),b=13.710(6),c=11.758(3) Å.Z=4,R F =0.038,R W = 0.037 for 1826 observed reflections. A variable temperature1H NMR study was also presented to demonstrate the solution fluxionality of5.