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Synthesis and Reactivity of Ester‐Functionalized 5‐Membered Rh I ‐κ 2 ‐C,O‐Chelates and Their Relevance in Rh(cod)‐Mediated Carbene Polymerization
Author(s) -
Finger Markus,
Lutz Martin,
Reek Joost N. H.,
de Bruin Bas
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100981
Subject(s) - chemistry , carbene , reactivity (psychology) , polymerization , ligand (biochemistry) , diene , chelation , olefin fiber , medicinal chemistry , 1,5 cyclooctadiene , polymer chemistry , stereochemistry , polymer , organic chemistry , catalysis , medicine , biochemistry , alternative medicine , receptor , natural rubber , pathology
The previous mechanistic studies of the Rh‐mediated polymerization of carbenes suggests the involvement of organometallic compounds that have been derived from Rh(diene) species that contain a five‐membered chelate ring of the type Rh{κ 2 ‐C,O‐[–CH(COOR)–CH(Pol)–C(OR)=O–]} (Pol = polymer chain), which are characterized by the coordination of the β‐ester group of the growing polymer chain to the metal. Herein we present our efforts to characterize the possibly related Rh I (cod){κ 2 ‐C,O‐[–CH(COOR)–CHR′–C(OR)=O–]} (cod = 1,5‐cyclooctadiene) species. These structures can be generated by means of olefin exchange with an allyl complex and with the concomitant release of the corresponding 1,3‐diene, which is derived from the allyl ligand. The product is unstable and further reacts by means of a bimolecular C–H activation process to form a related dinuclear complex [(cod)Rh(μ‐{–CH(COOR)–CH–C(OR)=O–}) 2 Rh(cod)], in which the carbon dianion of the dimethyl or diethyl succinate bridges two Rh(cod) moieties. The complex was synthesized in an independent way and was structurally characterized. We investigated the importance of these complexes in carbene polymerization.