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Stereochemically non-rigid transition metal complexes of 2,6-bis(phenyliminomethyl)pyridine and derivatives. Crystal structure of fac- ReBr(CO)(3)(PMTFA) (PMTFA=2,6-pyridylene-bis-(methylene-2-trifluoromethylaniline)

Creber, M. L., Orrell, K. G., Osborne, A. G., Sik, V., Bingham, A. L. and Hursthouse, M. B. (2001) Stereochemically non-rigid transition metal complexes of 2,6-bis(phenyliminomethyl)pyridine and derivatives. Crystal structure of fac- ReBr(CO)(3)(PMTFA) (PMTFA=2,6-pyridylene-bis-(methylene-2-trifluoromethylaniline) Journal of Organometallic Chemistry, 631, (1-2), pp. 125-134. (doi:10.1016/S0022-328X(01)01050-6).

Record type: Article

Abstract

The Schiff bases 2,6-bis(phenyliminomethyl)pyridine and its derivatives (L) form bidentate chelate complexes with transition metals Re-I, Pt-IV and Pd-II of general formulation fac-[ReBr(Co)(3)L], fac-[PtXMe3L] (X = Cl, Br or I), and cis-[Pd(p-CF3C6F4)(2)L]. In solution these complexes are stereochemically non-rigid, undergoing 1,4-metallotropic shifts and restricted rotations of the substituted aromatic rings attached to the metal-coordinated imino nitrogen. Rates and activation energies of these internal motions were measured by one-dimensional NMR bandshape analysis and two-dimensional EXSY NMR experiments over a range of solution temperatures. Free energy values, DeltaG(double dagger) (298.15 K), for the fluxional shifts were in the range 76-97 kJ mol(-1) with the Pd-II complexes having the lowest energies. An X-ray crystal structure of fac-[ReBr(CO)(3)PMTFA] (PMTFA = 2,6-pyridylene-bis(methylene-2-trifluoroaniline)) showed the pendant imine function to be in an E-conformation with its nitrogen trans to the pyridyl nitrogen.

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More information

Published date: 10 August 2001
Keywords: palladium(ii), platinum(iv), rhenium(i), fluxionality, dynamic nmr 2, 6-bispyridine bip, nmr, ligands, x=cl, br

Identifiers

Local EPrints ID: 19461
URI: http://eprints.soton.ac.uk/id/eprint/19461
ISSN: 0022-328X
PURE UUID: 12a85e30-0621-4fa2-b7ea-871cca0747df

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Date deposited: 13 Feb 2006
Last modified: 17 Jul 2017 16:31

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Contributors

Author: M. L. Creber
Author: K. G. Orrell
Author: A. G. Osborne
Author: V. Sik
Author: A. L. Bingham

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