Department of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland, 7602, South Africa.
Dalton Trans. 2009 Oct 21(39):8145-54. doi: 10.1039/b906840f. Epub 2009 Jul 22.
With the simplest of anionic Fischer-type carbene complexes acting as ligands, Cp(2)Zr(Cl){OCMe}M(CO)(5) compounds (M = Cr or W) promote alpha-olefin oligomerization and polymerization in the presence of MAO. Attaching an N-heterocyclic ring to the carbene carbon atom in similar precursors, allows a variety of hard metal ions and fragments to be captured by external bidentate coordination. The outcome of the attachment of a phosphorus or sulfur functionality to an alpha-carbon of an O-anionic carbene is formation of a bidentate ligand and then internal four-membered carbene-heteroatom chelate formation. alpha-Deprotonated carbene complexes are also precursors for remote, one-N, six-membered carbene complexes of various metals whereas alpha-C-, alpha-N- or alpha-O-deprotonated as well as beta-deprotonated Fischer-type carbene complexes display unique synthon properties towards Ph(3)PAu(+) and partake in unusual ensuing coordination of liberated group 6 metal carbonyl moieties to form dinuclear products.
最简单的阴离子费歇尔型卡宾配合物作为配体，Cp(2)Zr(Cl){OCMe}M(CO)(5)化合物（M = Cr 或 W）在 MAO 的存在下促进α-烯烃的齐聚和聚合。在类似的前体中将氮杂环卡宾碳原子连接到氮杂环上，允许各种硬金属离子和片段通过外部双齿配位捕获。磷或硫官能团与 O-阴离子卡宾的α-碳的连接的结果是形成双齿配体，然后是内部四元卡宾-杂原子螯合形成。α-去质子化的卡宾配合物也是远程、单 N、六元金属卡宾配合物的前体，而α-C-、α-N-或α-O-去质子化以及β-去质子化的费歇尔型卡宾配合物对 Ph(3)PAu(+)具有独特的前体性质，并参与释放的第六族金属羰基部分的不寻常后续配位，形成双核产物。
