The paper describes the preparation of new dinuclear Mo and W complexes bridged by Cp 6) are obtained by reaction of [W(CO) 3 -(NCMe) 3 ] with HCp 2 CpH or K 2 (Cp 2 Cp), respectively, as a cis-trans mixture of isomers which differ in the stereodisposition of the two metals with respect to the Cp 2 Cp system. cis-and trans-5 have been separated and reacted with CCl 4 to give [{W(CO) 3 Cl} 2 (µ-η 5 :η 5 -Cp 2 Cp)] (cis-or trans-7). Reaction of [{Mo(CO) 3 X} 2 (µ-η 5 :η 2), Cl (4)) with CN t Bu gives [{Mo(CO) 2 (CN t Bu)X} 2 (µ-η 5 :η 5 -Cp n Cp)] (8-11). Reaction of 9 with KH gives K 2 [{Mo(CO) 2 (CN t Bu)} 2 (µ-η 5 :η 5 -Cp 2 Cp)] ( 12). The cis isomers of the chloro derivatives 4, 7, or 11 are reduced to the dinuclear metal-metal-bonded complexes [{M-(CO) 2 L} 2 (µ-η 5 :η 5 -Cp 2 Cp)](MsM) (L ) CO, M ) Mo ( 13), W (15), L ) CN t Bu, M ) Mo ( 16)) by reaction with MeMgCl, whereas the trans isomer of 4 affords the polymer [{Mo(CO) 3 } 2 -(µ-η 5 :η 5 -Cp 2 Cp)] n (MosMo) (17). cis-2 reacts with H 2 O 2 to give a mixture of 13 and [{Mo-(CO) 3 } 2 {µ-η 5 :η 5 -(C 5 H 3 (SiMe 2 OH)SiMe 2 C 5 H 4 )}](MosMo) ( 14).
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