Bis(cyclopentadienyl)methan‐verbrückte Zweikernkomplexe, V. Heteronukleare Co/Rh‐, Co/Ir‐, Rh/Ir‐ und Ti/Ir‐Komplexe mit dem Bis(cyclopentadienyl)methan‐Dianion als Brückenliganden

Bis(cyclopentadienyl)methane‐bridged Dinuclear Complexes, V [1] . – Heteronuclear Co/Rh‐, Co/Ir‐, Rh/Ir‐, and Ti/Ir Complexes with the Bis(cyclopentadienyl)methane Dianion as Bridging Ligand * The lithium and sodium salts of the [C 5 H 5 CH 2 C 5 H 4 ] ‐ anion, 1 and 2 , react with [Co(CO) 4 I], [Rh(CO) 2 Cl] 2 , and [Ir(CO) 3 Cl] n to give predominantly the mononuclear complexes [(C 5 H 5 ‐CH 2 C 5 H 4 )M(CO) 2 ] ( 3, 5, 7 ) together with small amounts of the dinuclear compounds [CH 2 (C 5 H 4 ) 2 ][M(CO) 2 ] 2 ( 4, 6, 8 ). The 1 H‐ and 13 C‐NMR spectra of 3, 5 , and 7 prove that the CH 2 C 5 H 5 substituent is linked to the π‐bonded ring in two isomeric forms. Metalation of 5 and 7 with n BuLi affords the lithiated derivatives 9 and 10 from which on reaction with [Co(CO) 4 I], [Rh(CO) 2 Cl] 2 , and [C 5 H 5 TiCl 3 ] the heteronuclear complexes [CH 2 (C 5 H 4 ) 2 ][M(CO) 2 ][M′(CO) 2 ] ( 11–13 ) and [CH 2 (C 5 H 4 ) 2 ]‐[Ir(CO) 2 ][C 5 H 5 TiCl 2 ] ( 17 ) are obtained. Photolysis of 11 and 12 leads almost quantitatively to the formation of the CO‐bridged compounds [CH 2 (C 5 H 4 ) 2 ][M(CO)(μ‐CO)M′(CO)] ( 14, 15 ). According to an X‐ray crystal structure analysis the Co/Rh complex 14 is isostructural to [CH 2 (C 5 H 4 ) 2 ][Rh 2 (CO) 2 (μ‐CO)] ( 16 ).