Hydrocarbon‐bridged Metal Complexes, XXI. – Addition of Tetracarbonylosmate and ‐ruthenate to Coordinated Unsaturated Hydrocarbons: Trinuclear Complexes with two σ,α‐Allyl, Methylallyl, Cyclohexadiene, Cycloheptadiene, Cyclohexadienyl, Cycloheptatrien, and “Thiophene” Bridges The addition of organometallic nucleophiles [M(CO)₄]^2‐ (M = Os, Ru) to [(Cp)(ON)(OC)Mo(allyl)]⁺, [Cp(OC)₂Mo(butadiene)]⁺, [(OC)₃Fe(cycloheptadienyl)]⁺, [(OC)

Abstract

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

Heteropolymetallic Complex Syntheses by Reiterative Nucleophilic Additions of Lithiated (η6-Arene)tricarbonylchromium Compounds to Cationic (η6-Benzene)manganese Complexes

“…Indeed, Beck et al described the reaction of (η 6 -benzene)tricarbonylmanganese with deprotonated diphenyl methane or benzothiophene coordinated to tricarbonylchromium . They also observed the reactions with carbonyl osmate, carbonyl rhenate, and anionic alkynyl complexes 12e…”

Manganese Hydrocarbon Complexes Excluding Cyclopentadienyl

“…8 Reaction of cation (1) with the tetracarbonylosmium dianion provides the bis[(t| 5 -cyclohexadienyl)manganese]tetracarbonylosmium complex (5), a rare example o f the reaction of a transition metal nucleophile with a transition metal 7i-complex (Equation (3)). 9 Substitution of a carbon monoxide ligand by phosphites has also been reported, and electrocatalytic carbon monoxide substitution by phosphites is chemically irreversible up to a range of 20 V s .°N …”

“…13 " 22 Alkoxy substituents have been examined in detail, with attack occurring preferentially meta to the electron-rich substituent. For example, reaction o f Grignard reagents with (r| 6 -arene)manganese complex (9) generates products resulting f r o m attack only at the two meta positions (Equation (5)). Surprisingly, reaction at the more hindered meta position to produce (r| 5 -cyclohexadienyl)manganese complex (10) predominates with methylmagnesium bromide.…”

Reactivity of Metallophosphide Anions with Electrophilic (Arene)tricarbonylmetal Complexes

“…Beck et al, for example, described the reactivity of Mn complexes with deprotonated diphenylmethane or benzothiophene coordinated to Cr(CO) 3 , [3] as well as with carbonylosmate, [4] carbonylrhenate [5] and anionic alkynyl complexes. [6] More recently, Sweigart et al [7] demonstrated that a weak nucleophile such as [Pt(PPh 3 ) 2 (C 2 H 4 )] could cleave a strained CϪC bond in the four-membered ring of biphenylene coordinated to an Mn(CO) 3 ϩ fragment, giving the insertion product.…”

“…In the Cr series, strongly nucleophilic organometallic anions [such as Fe(CO) 4 2Ϫ , M(CO) 5 2Ϫ , M ϭ Cr, W, CpFe(CO) 2 Ϫ ] reacted with [(C 6 H 5 X)Cr(CO) 3 ], allowing the formation of dinuclear complexes, which arise as a result of halogen substitution by the organometallic anions. [12] This has led us to investigate the reaction of metallophosphide anions with (η 6 -arene)metal complexes, and for this purpose we have selected the [(CO) x MЈPPh 2 ] Ϫ anions.…”