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

Abstract

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.

Redox Chemistry of [Co4(CO)3(μ3-CO)3(μ3-C7H7)(η5-C7H9)] – Reversible Carbon−Carbon Coupling versus Metal Cluster Degradation

“…The bond C1ϪC21, which joins the two seven-membered rings, is slightly longer [1.570(6) Å ] than would be expected for a single bond. This value compares well with the corresponding bond lengths in the dinuclear complexes [{(CO) 3 Fe} 2 {µ-η 4 :η 4 -(C 7 H 9 ) 2 }] [1.564(4) Å ] [21] and [{(η-C 5 H 5 )Co} 2 {µ-η 4 :η 4 -(C 7 H 9 ) 2 }] (10) [1.564(5) Å ]. [22] Within the limitations of the experimental accuracy, the geometry of the Co 4 (CO) 6 cluster units in [4A] 2؊ is quite similar to that seen in other complexes containing the Co 4 (CO) 6 (µ 3 -C n H n ) moiety.…”

Structure and Reactivity of Early−Late Heterobimetallic Complexes

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18 Crystal structure of [{(OC) 3 Mo(μ-C 7 H 7 )} 2 Os(CO) 4 ]. Reprinted from ref . Copyright 1991 Wiley-VCH Verlag GmbH.

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Manganese Alkyls and Hydrides

“…The anion [Mn(CO) 5 ]~ adds stereospecifically to the allyl terminus cis to NO in the exo rotamer of T t -a l l y l cation (30) (Equation (10)). 55 In a similar manner, complexes (32) 56 and (33) …”

“…In some cases, [Mn(CO) 5 ]~ reacts with cationic 7i-complexes via apparent electron transfer, resulting in C-C coupling of the two reduced cations without the incorporation of manganese 56. …”