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The additive reaction of SbCl_3 to trimolybdenum clusters with loose coordination sites,Mo_3 (μ_3-S)(μ-S)_3 [S_2P (OEt)_2]_4·L′(1L′=H_2O; 2, L′=C_3H_3ON), in a C_2H_5OH-HCl medium yieldscomplexes {Mo_3 (μs-S) [(μ-S)_3·SbCl_3] [S_2P (OEt)_2]_4·(C_2H_6OH)}(C_2H_5OH) (3) and {Mo_3 (μ_3-S) [(μ-S)_3·SbCl_3] [S_2P (OEt)_2]_3 [SXP (OEt)_2] · (C_3H_3ON)} (X=S,O) (4), respectively. The crystal and mo-lecular structures of these two compounds have been determined by single crystal X-ray crystallography:crystal 3 belongs to the monoclinic system, P2_1,/n, while crystal 4 belongs to the trielinic system, P1,The intensity data were collected on an Enraf-Nonius CAD-4 diffractometer with graphite-monochro-matized MoKα radiation by using the ω-2θ technique. The structures were solved by the Pattersonmethod as well as direct methods and refined by full matrix least-squares method. Final R values were0.078 for crystal 3 and 0.068 for crystal 4, respectively. The result of the structure determination showedthat the two molecular structures are practically formed by connecting a trimolybdenum clusterswith loose coordination sites,{Mo_3 (μs-S) (μ-S)_3 [S_2P(OEt)_2]_4·L (L=C_2H_5OH, C_3H_3ON), with a SbCI_3molecule through three (μ-S)atoms to form the {Mo_3SbS_4} core of a cubane-like type. There arerelatively weak coordination bonds between the Sb and the three (μ-S) atoms, while no bonding in-teraction between the Sb and the three Mo atoms is found. In the additive compounds the structuralcharacter of the trimolybdenum clusters with loose coordination sites has significantly been changed.In addition, 3 still has the reactivity for the loosely coordinated EtOH to be replaced by an oxazole ringto form crystal 4. However, the three (μ-S) atoms may be regarded as triple bridging S atoms eachconnecting two Mo atoms and a Sb atom. The information obtained serves as an evidence that thetetranuclear clusters might be formed by a [3+1] reaction mode.
The additive reaction of SbCl_3 to trimolybdenum clusters with loose coordination sites, Mo_3 (μ_3-S) (μ-S) _3 [S_2P (OEt) _2] _4 · L ’(1L’ = H_2O; 2, L ’= C_3H_3ON) in a C_2H_5OH-HCl medium yieldscomplexes {Mo_3 (μs-S) [(μ-S) _3 · SbCl_3] [S_2P (OEt) _2] _4 · (C_2H_6OH) (C_2H_5OH) (3) and {Mo_3 ) [(μ-S) _3 · SbCl_3] [S_2P (OEt) _2] _3 [SXP (OEt) _2] · (C_3H_3ON)} (X = S, O) structures of these two compounds have been determined by single crystal X-ray crystallography: crystal 3 belongs to the monoclinic system, P2_1, / n, while crystal 4 belongs to the trielinic system, P1, The intensity data were collected on an Enraf-Nonius CAD-4 diffractometer with graphite-monochro-matized MoKα radiation by using the ω-2θ technique. The structures were solved by the Patterson method as well as direct methods and refined by full matrix least-squares method. Final R values were 0.078 for crystal 3 and 0.068 for crystal 4, respectively. The result of the structu re determination showed that the two molecular structures are practically formed by connecting a trimolybdenum clusters with loose coordination sites, {Mo_3 (μs-S) (μs) _3 [S_2P (OEt) _2] _4 · L (L = C_2H_5OH, C_3H_3ON) There arerelatively weak coordination bonds between the Sb and the three (μ-S) atoms, while no bonding in-tectonic interaction between the (Mo-3SbS_4} core to a cubane- the Sb and the three Mo atoms is found. In the additive compounds the structural character of the trimolybdenum clusters with loose coordination sites has significantly been changed.In addition, 3 still has the reactivity for the loosely coordinated EtOH to be replaced by an oxazole ring to form crystal 4. However, the three (μ-S) atoms may be deemed as triple bridging S atoms each connected two Mo atoms and a Sb atom. The information obtained serves as an evidence that the tetragonal clusters might be formed by a [3 + 1] reaction mode.