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Stereochemically non-rigid transition metal complexes of2,6-bis[(1-phenylimino)ethyl]pyridine (BIP)Part 2. Dynamic NMR studies of fac-[ReX(CO)3(BIP)](X = C1, Br, or I).Crystal structure of fac-[ReBr(CO)3(BIP)]

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Orrell, KG, Osborne, AG, Sik, V, Webba da Silva, Mateus, Hursthouse, MB, Hibbs, DE, Abdul Malik, KM and Vassilev, NG (1997) Stereochemically non-rigid transition metal complexes of2,6-bis[(1-phenylimino)ethyl]pyridine (BIP)Part 2. Dynamic NMR studies of fac-[ReX(CO)3(BIP)](X = C1, Br, or I).Crystal structure of fac-[ReBr(CO)3(BIP)]. Journal of Organometallic Chemistry, 538 . pp. 171-183. [Journal article]

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Abstract

The complexes fac-[ReX(CO)3(BIP)] (X = CI, Br or I; BIP = 2,6-bis[(1-phenylimino)ethyl]pyridine) have been synthesised andcharacterised as involving BIP as a bidentate chelate ligand. In solution the ligand exists in three conformational forms, namely E,E- andboth distal and proximal E,Z-isomers. 2D-EXSY NMR has been used to measure 1,4-metallotropic shifts of the ReX(CO) 3 moietybetween equivalent E,E forms, E,Z-isomerisation of the pendant imine function and restricted C-C rotation of the pendant arm of theBIP ligand. Activation energies AG * (298.15 K) for all these processes are of comparable magnitude, in the range 79-88 kJmol-J, andare essentially halogen independent. Restricted rotation of the phenyl ring attached to the Re-coordinated nitrogen was also detected withAG * = 67.3 + 0.2 kJ mol- i. A crystal structure of fac-[ReBr(CO)3(BIP)] confirms the E-conformation of the pendant imine functionwith its N atom cis to the pyridyl nitrogen.

Item Type:Journal article
Faculties and Schools:Faculty of Life and Health Sciences
Faculty of Life and Health Sciences > School of Pharmacy and Pharmaceutical Science
Research Institutes and Groups:Biomedical Sciences Research Institute
Biomedical Sciences Research Institute > Molecular Medicine
Biomedical Sciences Research Institute > Molecular Medicine > Transcriptional Regulation & Epigenetics
ID Code:18307
Deposited By:Dr Mateus Webba da Silva
Deposited On:03 May 2011 10:07
Last Modified:04 Dec 2012 14:33

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