Reductive coupling of phenylfulvene with amalgamated calcium metal followed by hydrolysis yields CpPhCHCHPhCp (1) in high yield. Refluxing ligand 1 and Fe(CO)5 in xylene produces (PhCHCHPh)-coupled bis(cyclopentadienyl) tetracacrbonyl dirron (PhCHCHPh)[(η5-C5H4)Fe(CO2]2 (2) as a mixture of meso (2-meso) and racemis isomers (2-rac). The pure reacmic isomers of the Mo and W analogues (3-rac and 4-rac) have been synthesized by lithiation of ligand 1 and addition of (MeCN)3M(CO)3(M=Mo,W) followed by oxidation with 2 equiv. of ferrocenium tetrafluroborate. All the new complexs have been fully charac-terrized. The meolecular structure of 1-meso, 2-meso, 2-rac, 3-rac, and 4-rac have been determinde by X-ray diffraction analysis.

Reactions of CpArCHCHArCp [Ar=Ph (1), p-MeOC6H4 (2)] with Ru3(CO)12 in refluxing xylene afforded the unexpected bridgeing C-C cleavage and cyclopentadienyl coupling products: the 2,2'-bisubstituted fulvalene diruthenium complexes (η5:η5-2,2'-ArCH2C5H3C5H3CH2Ar)Ru2(CO)4 [Ar=Ph (5),p-MeOC6H4 (9)] and the partially hydorgented products (η5:η3-ArCH2C5H3C5H6CHAr)Ru2(CO)4 [Ar=Ph(4), p-MeOC6H4 (8)], in addition to the normal bridged bis(cyclopentadienyl) tetracarbonyl diruthenium complexes (ArCHCHAr)[η5-C5H4)Ru(CO)]2(μ-CO)2[Ar=Ph(7),p-MeOC6H4 (10)]. When ligand (tBuC5H4)PhCHCHPh(tBuC5H4) (3) reacted with Ru3(CO)12, the tetrasubstituted fulvalene diruthenium complex (η5:η5-PhCH2tBuC5H2C5H2tBuCH2Ph)Ru2(CO)4 (11) and three normal bridged bis-(cyclopentadienyl) diruthenium complexes (PhCHCHPh)[(η5-tBuC5H3)Ru(CO)]2(μ-CO)2 (12-14) were obtained. The molecular structures of 4, 5, 7-meso, 7-rac, 8, 10-meso, 11, 12, 13, and 14 were determined by X-ray diffraction. The stereochemistry of the reaction was also studied, and the possible mechanism was discussed.

合成了一系列亚环烷基桥连环戊二烯基茂金属化合物（CH2）nC（C5H4）2MCI2[M=Ti，n=4（4），5（5），6（6）; M=Zr，n=4（10）、5（11）、6（12）]，用甲基铝氧烷（MAO）作助催化剂研究了其催化乙烯聚合反应。其中亚环烷基桥连环戊二烯基钛化合物的催化活性远高于相应的锆和铪类似物，且在较高温度显示其最高活性。为进行对比，合成了亚硅杂环戊基桥连环戊二烯基茂金属化合物（CH2）4Si（C5H4）2MCI2（M-Ti，Zr）和亚异丙基桥连环戊二烯基茂金属化合物Me2C（C5H4）2MCI（M=Ti，Zr）并用于催化乙烯聚合。在这两种催化剂中，钛化合物的催化活性都远离于相应的锆类似物，尤其是在较低温度下。用X-射线衍射分析测定了化合物4～9的晶体结构。对催化剂结构与催化活性的关系，特别是桥链的影响进行了讨论。

The indenyl iron compound (η5-C9H7)Fe(η5-C5H5) (1) was found to react with benzyne, generated from o-trimethylsilylphenyl triflate by fluoride-induced 1, 2-elimination, to afford the Diels-Alder adduct 1,2-(1,4-dihydro-naphthalen-1,4-diyl)ferrocene (2). When the bis-(indenyl) iron complexes (η5-R-C9H6)2Fe [R=H(3); 2-Me(6); 1-SiMe3(9)] reacted with benzyne, the bisadducts [R=H(5); 2-Me(8); 1-SiMe3(11)] were obtained along with the corresponding monoadducts [R=H(4); 2-Me(7); 1-SiMe3(10)]. The reaction of teramethyl-dislyene-bridged bis(indenyl) iron (Me2SiSiMe2)(η5-C9H6)2Fe(12) with benzyne gave only the monoadduct (13). Complex 2 was also tested for ring-opening metathesis polymerization (ROMP) in the presence of Grubbs' catalyst [(PCy3)2RuCl2=CHPh] but was found to be inactive under normal conditions. The molecular structures of 2, 5, 8, and 13 have been determinde by X-ray diffraction.

Thermal treatment of the prydyl side-chain-func-tionalized cyclopentadiense with Fe(CO)5 and Ru3(CO)12 gave different intramolecular C-H activated products, in addittion to the normal dinuclear metal complexs. Reactions of the dinuclear metal complexs with I2 also gave different metal iodide complexes.