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学科主题: 金属有机化学
题名: Unexpected metallosite-selective CO substitution of heteronuclear tetrahedral (μ3-S)FeCoM(M=Mo,W) carbonyl clusters with cyclohexyl isocyanide: 59Co NMR and ~57Fe Mossbauer spectra of(μ3-S)FeCoMo(CO)^8-n(η~5-C^5H^4COMe)(C^6H^11NC)n(n=1-3) and crystal structures of (μ3-S)FeCoM(CO)^8-n(η~5-C^5H^4R)(C^6H^11NC)n(M=Mo,W;R=MeCO,MeO^2C;m=1,2)
其他题名: 杂核四面体(μ^3-S)FeCoMe(M=Mo,W)羰基原子簇与环己苯异氰化物的新奇金属位置选择性CO取代反应(μ3-S)FeCoMo(CO)^8-n(η~5-C^5H^4COMe)(C^6H^11NC)n(n=1-3的59CoNMR和57Fe的Mossbauer 光谱和 (μ3-S)FeCoM(CO)^8-n(η~5-C^5H^4R)(C^6H^11NC)n(M=Mo,W;R=MeCO,MeO^2C;m=1,2)的晶体结构
作者: 宋礼成 ; 胡青眉 ; 陈家碧 ; 王红根
通讯作者: 宋礼成
刊名: Organometallics
发表日期: 2001-01-01
卷: 20, 期:22, 页:4510-4516
收录类别: SCI
部门归属: 中国科学院上海有机化学研究所金属有机化学开放实验室; 南开大学化学系
摘要: We have first studied the selective CO substitution reactions of heteronuclear tetrahedral clusters of the type (μ3-S)FeMCo(CO)^8(η~5-C^5H^4R)(M=Mo,W)with cyclohexyl isocyanide CyNC. It was found that while clusters(μ3-S)FeMCo(CO)^8(η~5-C^5H^4R)(M=Mo,W;R=MeCO)react with 1 equiv of CyNC in THF at room temperature to give mono-CyNC-substituted products (μ3-S)FeMCo(CO)^7(CyNC)(η~5-C^5H^4COMe)(1a,M=Mo;1b,M=W)in 63% and 79% yields, clusters of (μ3-S)FeMCo(CO)^8(η~5-C^5H^4R)(M=Mo,W;R=MeCO,MeO^2C,H)react with 2 equiv of cyNC under similar conditions to afford di-CyNC-substituted products (μ3-S)FeMCo(CO)^6(CyNC)^2(η~5-C^5H^4R)(2a,M=Mo;R=MeCO;2b,M=W,R=MeCO;2c,M=Mo,R=MeO^2C;2d,M=W,R=MeO^2C;2eM=MoR=h)in 56-68% yields. Similarly, tri-CyNC-substituted derivatives (μ3-S)FeMoCo(CO)^5(CyNC)^3(η~5-C^5H^4R)(3a,R=MeCO;3b,R=MeO^2C)are produced by reaction of clusters (μ3-S)FeMoCo(CO)^8(η~5-C^5H^4R)(R=MeCO,MeO^2C)with 3 equiv of CyNC in 37% and 39% yields. The combined use of spectroscopic techniques (IR, ~1H and ~59Co NMR, and ~57Fe Mossbauer spectroscopy) with crystal X-ray diffraction analyses for 1a, b and 2c d has established that the CyNC ligand in 1a, b is bonded to M (M=Mo,W), the two CyNC ligands in 2a-e are bound to M(Mo, W)and Fe, and the three CyNC ligands in 3a b are attached to Mo, Fe, and Co, respectively. Thus, the metallosite selectivity toward CyNCin the reaction of this type of cluster system decreases obviously in the order of η~5-RC^5H^4(CO)^2M(M=Mo,W) >Fe(CO)^3>Co(CO)^3
语种: 英语
相关网址: 查看原文
内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/22294
Appears in Collections:金属有机化学国家重点实验室_期刊论文

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Recommended Citation:
宋礼成,胡青眉,陈家碧,等. Unexpected metallosite-selective CO substitution of heteronuclear tetrahedral (μ3-S)FeCoM(M=Mo,W) carbonyl clusters with cyclohexyl isocyanide: 59Co NMR and ~57Fe Mossbauer spectra of(μ3-S)FeCoMo(CO)^8-n(η~5-C^5H^4COMe)(C^6H^11NC)n(n=1-3) and crystal structures of (μ3-S)FeCoM(CO)^8-n(η~5-C^5H^4R)(C^6H^11NC)n(M=Mo,W;R=MeCO,MeO^2C;m=1,2)[J]. Organometallics,2001,20(22):4510-4516.
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