Stable crystalline annulated diaminocarbenes: coordination with rhodium(I), iridium(I) and catalytic hydroformylation studies

Dastgir, Sarim; Coleman, Karl S.; Cowley, Andrew R.; Green, Malcolm L.H.

Abstract

Stable annulated diaminocarbene ligands 7,9-bis(2,4,6-trimethylphenyl)-6b,9a-dihydroace naphtha[1,2-d]imidazolin-2-ylidene and 7,9-bis(2,6-diisopropylphenyl)-6b,9a-dihydroacenaphtho-[1,2-d]imidazolin-2-ylidene; designated as (BIAN-SIMes, 5a,) and (BIAN-SIPr, 5b), respectively, have been prepared. The base dependent decomposition of imidazolinium salts via ring opening at the backbone was also observed. The corresponding rhodium(I) and iridum(I) complexes (eta(4)-1,5-COD)M(BIAN-SIMes) Cl and (eta(4)-1,5-COD)M(BIAN-SIPr)Cl; M = Rh (6a, 6b) and Ir (7a, 7b) have been synthesised by the reaction of free carbene with [M(eta(4)-1,5-COD)(mu-Cl)](2); where M = Rh, Ir. The cationic Ir(I) complexes [(eta(4)-1,5-COD)Ir(BIAN-SIMes)Py]BF(4) 8a and [(eta(4)-1,5-COD)Ir(BIAN-SIPr)Py]PF(6) 8b have also been synthesised. Compounds 4b, 5a, 6a, 6b, 7b and 8b have been structurally characterised. The catalytic activities for the rhodium(I) complexes 6a and 6b were evaluated for the hydroformylation of 1-octene.

Citation

Dastgir, S., Coleman, K. S., Cowley, A. R., & Green, M. L. (2009). Stable crystalline annulated diaminocarbenes: coordination with rhodium(I), iridium(I) and catalytic hydroformylation studies. Dalton Transactions, 7203-7214. https://doi.org/10.1039/b905729c

• Journal Article Type: Article
• Publication Date: 2009
• Deposit Date: May 21, 2014
• Journal: Dalton Transactions
• Print ISSN: 1477-9226
• Electronic ISSN: 1477-9234
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Issue: 35
• Pages: 7203-7214
• DOI: https://doi.org/10.1039/b905729c
• Keywords: n-heterocyclic carbene transition-metal-complexes x-ray-structure diolefin complexes structural characterization organometallic catalysis hydrogenation catalysts nucleophilic carbenes ligand imidazol-2-ylidene