Use of palladium-catalyzed coupling reactions in the synthesis of heterobimetallic complexes. Preparation of bis(cyclopentadienyl)acetylene heterodinuclear complexes

• Published in: Organometallics 1990-03, Vol.9 (3), p.687-694
• Main Authors: Lo Sterzo, Claudio, Stille, J. K
• Format: Article
• Language: English
• Subjects: 400201 - Chemical & Physicochemical Properties; ALKENES; CATALYSIS; Chemistry; Condensed matter: structure, mechanical and thermal properties; CRYSTAL STRUCTURE; CYCLOALKENES; CYCLOPENTADIENE; DATA; DATA ANALYSIS; DIENES; ELEMENTS; Exact sciences and technology; EXPERIMENTAL DATA; HOMOGENEOUS CATALYSIS; HYDROCARBONS; INFORMATION; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; IRON; MANGANESE; MEASURING INSTRUMENTS; MEASURING METHODS; METALS; NUMERICAL DATA; Organic chemistry; ORGANIC COMPOUNDS; ORGANOMETALLIC COMPOUNDS; Organometalloidal and organometallic compounds; PALLADIUM; Physics; PLATINUM METALS; POLYENES; Preparations and properties; RHENIUM; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; SYNTHESIS; TRANSITION ELEMENTS; Transition metals derivatives; TUNGSTEN
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om00117a025

The palladium-catalyzed coupling reactions of {eta}{sup 5}-iodocyclopentadienyl complexes of Fe, W, Mn, and Re with Bu{sub 3}SnC{triple bond}CH yield the corresponding {eta}{sup 5}-ethynylcyclopentadienyl derivatives ({eta}{sup 5}-HC{triple bond}CC{sub 5}H{sub 4})ML{sub n} (M = Fe, W, Mn, Re). Upon reaction with Et{sub 2}NSnR{sub 3} (R = Me, Bu), the acetylenic proton is replaced with a trialkyltin group, forming the {eta}{sup 5}((trialkylstannyl)ethynyl)cyclopentadienyl derivatives ({eta}{sup 5}-R{sub 3}SnC{triple bond}CC{sub 5}H{sub 4})ML{sub n}. A second palladium-catalyzed coupling reaction between these trialkyltin derivatives and ({eta}{sup 5}-iodocyclopentadienyl)metal complexes affords the heterobimetallic complexes L{sub n}M({eta}{sup 5}-C{sub 5}H{sub 4})C{triple bond}C({eta}{sup 5}-C{sub 5}H{sub 4})M{prime}L{sub m} (M and M{prime} = Fe, W, Mo, Mn, Re). The crystal structure of Ph{sub 3}P(CO){sub 2}Mn({eta}{sup 5}-C{sub 5}H{sub 4})C{triple bond}C({eta}{sup 5}-C{sub 5}H{sub 4})W(CO){sub 3}CH{sub 3} confirmed the general structure of these heterobimetallic complexes.