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The reactivities of Mo cluster——A selective substitution reaction of the bridging(dtp)ligand and the crystal structure of{Mo_3S_4(μ-O_2CR)(dtp)_3(Py)}

The reactivities of Mo cluster——A selective substitution reaction of the bridging(dtp)ligand and the crystal structure of{Mo_3S_4(μ-O_2CR)(dtp)_3(Py)}
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摘要 The reaction of trinuclear molybdenum cluster{Mo_3S_4(μ-dtp)(dtp)_3(H_2O)}1[dtp= S_2P(OEt)_2]with RCO_2Na(R=H,CH_3)in the presence of Py gave the black compounds{Mo_3S_4(μ- O_2CR)(dtp)_3(Py)}(2,R=H,3,R=CH_3).Both compounds are characterized by X-ray crystallo- graphy.It is shown that crystals 2 and 3 belong to space group P with Z=2 and a=10.519(2),b= 12.121(2),c=15.757(2),α=93.27(1),β=94.63(1),γ=105.22(1)°,V=1925~3 for crystal 2,whereas a=9.556(2),b=14.067(7),c=15.914(9),α=101.41(4),β=101.44(4),γ=74.26(3)°,V=1994~3 for crystal 3.The final R factors are 0.041 and 0.048 for crystal 2 and 3 respectively.The structure analysis indicates that(O_2CR)^- ligand selectively substitutes the bridging(dtp)ligand.This type of Mo_3 cluster molecule where structure contains two species of bidentate ligand is for the first time to be obtained by us. The reaction of trinuclear molybdenum cluster{Mo_3S_4(μ-dtp)(dtp)_3(H_2O)}1[dtp= S_2P(OEt)_2]with RCO_2Na(R=H,CH_3)in the presence of Py gave the black compounds{Mo_3S_4(μ- O_2CR)(dtp)_3(Py)}(2,R=H,3,R=CH_3).Both compounds are characterized by X-ray crystallo- graphy.It is shown that crystals 2 and 3 belong to space group P with Z=2 and a=10.519(2),b= 12.121(2),c=15.757(2),α=93.27(1),β=94.63(1),γ=105.22(1)°,V=1925~3 for crystal 2,whereas a=9.556(2),b=14.067(7),c=15.914(9),α=101.41(4),β=101.44(4),γ=74.26(3)°,V=1994~3 for crystal 3.The final R factors are 0.041 and 0.048 for crystal 2 and 3 respectively.The structure analysis indicates that(O_2CR)^- ligand selectively substitutes the bridging(dtp)ligand.This type of Mo_3 cluster molecule where structure contains two species of bidentate ligand is for the first time to be obtained by us.
出处 《Acta Chimica Sinica English Edition》 SCIE CAS CSCD 1989年第1期24-36,共1页
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