Synthesis, Structure, and Temperature-Dependent Dynamics of Neutral Palladium Allyl Complexes of Annulated Diaminocarbenes and Their Catalytic Application for C-C and C-N Bond Formation Reactions

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

Abstract

Imidazolinium salts 7,9-bis(2,4,6-trimethylphenyl)-6b,9a-dihydroacenaphtho[1,2-d]imidazolinium tetrafluoroborate and 7,9-bis(2,6-diisopropylphenyl)-6b,9a-dihydroacenaphtho[1,2-d]imidazolinium tetrafluoroborate, designated as [(BIAN-SIMes)(H)]BF(4) (3a) and [(BIAN-SIPr)(H)]BF(4) (3b), respectively, have been prepared and structurally characterized. The molecular structure of 3a shows the presence of a bifurcated hydrogen bond between the tetrafluoroborate anions and the central imidazolinium proton (-NCHN-). The palladium(II) complexes (eta(3)-C(3)H(5))Pd(BIAN-SIMes)Cl (5a) and (eta(3)-C(3)H(5))Pd(BIAN-SIPr)Cl (5b) have been synthesized. The temperature-dependent NMR behavior of sigma-bonded palladium(II) complex 5b was studied. The crystal structure of 5b shows a localized single and double bond between the allyl ligand. The catalytic activities of the palladium(II) complexes 5a and 5b have been evaluated for Suzuki-type C-C coupling and for room-temperature C-N bond formation using aryl halides.

Citation

Dastgir, S., Coleman, K. S., Cowley, A. R., & Green, M. L. (2010). Synthesis, Structure, and Temperature-Dependent Dynamics of Neutral Palladium Allyl Complexes of Annulated Diaminocarbenes and Their Catalytic Application for C-C and C-N Bond Formation Reactions. Organometallics, 29(21), 4858-4870. https://doi.org/10.1021/om1000327

• Journal Article Type: Article
• Publication Date: 2010
• Deposit Date: May 21, 2014
• Journal: Organometallics
• Print ISSN: 0276-7333
• Electronic ISSN: 1520-6041
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 29
• Issue: 21
• Pages: 4858-4870
• DOI: https://doi.org/10.1021/om1000327
• Keywords: heterocyclic carbene ligands transition-metal-complexes cross-coupling reactions copper(ii) complexes aryl halides pi nhc conversion reactivity olefin
• Public URL: https://durham-repository.worktribe.com/output/1432664