Reactions of 5-Carbon and Larger Ligands

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.

Kohlenwasserstoffverbrückte Komplexe XX Nucleophile Addition von Carbonylmetallaten an kationische Hexadienyl‐, Cycloheptadienyl‐, Cycloheptadienyl‐ und Cyclooctadienyl‐Komplexe von Eisen und Ruthenium: Heterodimetall‐Komplexe mit η¹:η⁴‐C₆‐, ‐C₇‐ und ‐C₈‐Kohlenwasserstoffbrücken

Niemer¹,

Breimair²,

Wagner³

et al. 1991

Kohlenwasserstoffverbrückte Komplexe, XXVII. C—C‐Kupplung von ungesättigten Kohlenwasserstoffen in anionischen und kationischen Komplexen. Addition der Anionen von μ1‐(Diphenylmethan)1‐, μ1‐Fluoren‐und μ1‐(9,10‐Dihydroanthracen)1‐bis(tricarbonylchrom) an koordinierte Olefin‐, Benzol‐, Cyclohexadienyl‐, Cycloheptadienyl‐und Cycloheptatrienyl‐Liganden

Wieser¹,

Karaghiosoff²,

Beck³

1993

Kohlenwasserstoffverbrückte Komplexe, XXX. Nucleophile Addition von Carbonylmetallaten an kationische Vinyl‐, Dien‐, Dienyl‐ und Trien‐Komplexe von Eisen, Ruthenium und Cobalt: Zwei‐, drei‐, vier‐ und fünfkernige Komplexe mit σ,σ‐ und σ,π‐Kohlenwasserstoffbrücken

Hüffer¹,

Wieser²,

Polborn³

et al. 1994

Hydrocarbon‐Bridged Complexes, XXX. — Nucleophilic Addition of Carbonylmetallates to Cationic Vinyl, Diene, Dienyl and Triene Complexes of Iron, Ruthenium and Cobalt: Di‐, Tri‐, Tetra‐ and Pentametallic Complexes with σ,σ‐ and σ,π‐Hydrocarbon Bridges The reactions of [Re(CO)5]−, [Ru(CO)2Cp]−, and [Os(CO)4]2− with [Cp2(OC)2Fe2(μ‐CO)(μ‐η1:η2‐CH=CH2)]+, [Cp*Ru(η2:η4‐1,3,7‐octatriene)]+, [(OC)Fe(η4‐diene)(η5‐cycloheptadienyl)]+, and [CpCo(η5‐cyclodienyl)]+ give the nucleophilic adducts whereas with [Mn(CO)5]−, [W(CO)3Cp]−, and [Fe(CO)2Cp]− formation of the corresponding C‐C coupling products and of the metal‐metal‐bonded dimers is observed. The structures of Cp*Ru(μ‐η1:η2:η3‐1,5‐octadienyl)Re(CO)5 (4), [Cp* Ru(μ‐η1:η2:η3‐1,5‐octadienyl)]2Os(CO)4 (6), and of (OC)‐Fe(η4‐1,3‐cyclohexadiene) (μ‐η1:η4‐1,3‐cycloheptadiene)Re(CO)5 (9) have been determined by X‐ray diffraction.