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Hydrocarbon‐Bridged Metal Complexes, XX. – Nucleophilic Addition of Carbonyl Metallates to Cationic Hexadienyl, Cyclohexadienyl, Cycloheptadienyl, and Cyclooctadienyl Complexes of Iron and Ruthium: Heterobimetallic Complexes with η1:η4, ‐C6, ‐C7, and ‐C8 Hydrocarbon Bridges The addition of Re(CO)‐5, Mn(CO)‐5, and [(η5‐C5H5)W(CO)3]‐ to the cationic dienyl complexes [(η5‐dienyl)M(CO)3]+ (M = Fe, Ru; dienyl = hexadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, bicyclo[5.1.0]octadienyl) gives the heterobimetallic η1:η4‐hydrocarbon‐bridged complexes 1 – 4, 6, 7. In solution the initial nucleophilic adduct 2e of [(η5‐cyclo‐hexadienyl)Ru(CO)3]+ and [Re(CO)5]‐ rearranges to the complex 3, in which the Re(CO)5 group is bound to a sp2 carbon atom. By using Mn(CO)‐5 also the products of electron transfer between cation and anion have been observed. The crystal structures of (OC)3Fe(μ‐η4:η1‐hexadiene)Re(CO)5 (1), (OC)3Ru(μ‐η4:η1‐cyclohexadiene)Re(CO)5(3), (OC)3Fe(η4:η4‐C7H9—C7H9)Fe(CO)3 (5), (OC)3Ru(μ‐η4:η1‐cyclooctadiene)Re‐(CO)5 (6b), and of (OC)3Fe(η4:η1‐bicyclo[5.1.0]octadiene)‐Re(CO)5 (7) have been determined by X‐ray diffraction.

Addition von Tetracarbonylosmat und -ruthenat an koordinierte ungesattigte Kohlenwasserstoffe: Dreikernige Komplexe mit zwei o,n-Allyl-, Methylallyl-, Cyclohexadien-, Cycloheptadien-, Cyclohexadienyl-, Cycloheptatrien-und ,,Thiophen"-Brucken

der Ziegler-Natta-Polymerisation von Ethylen 61, der Platin-katalysierten Umlagerung von Kohlenwasserstoffen 7, und der OlefinMetathese*).C2-Verbruckte Komplexe sind vom Typ A -C bekannt.

Hydrocarbon‐Bridged Metal Complexes, XXII1). – Addition of Anionic Fischer Carbene Complexes to Coordinated Unsaturated Hydrocarbons with C – C Coupling The addition of [(OC)5MC(OMe)CH2]– (M = Cr,W) to the cationic complexes [(OC)5Re(C2H4)]+ and [(OC)3M' (λ7‐C7H7)]+ (M' = Cr, Mo) affords the bimetallic hydrocarbon‐bridged complexes (OC)5M = C(OMe)CH2CH2CH2Re(CO)5 (1) and (OC)5M = C(OMe)CH2C7H7 – λ6 – M'(CO)3 (2), respectively. The structures of 1a and 2d have been determined by X‐ray diffraction.