The coordination chemistry of enantiopure diimines derived from 1-phosphanorbornadiene-2-carboxaldehydes |
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Authors: | Alexandre Germoni Louis Ricard François Mathey |
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Institution: | a Laboratoire “Hétéroéléments et Coordination” UMR CNRS 7653, DCPH, Ecole Polytechnique, 91128 Palaiseau Cedex, France b UCR-CNRS Joint Research Chemistry Laboratory, Department of Chemistry, University of California Riverside, Riverside, CA 92521-0403, USA |
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Abstract: | The reaction of trans-1,2-diaminocyclohexane with enantiopure (R)-2-formyl-1-phosphanorbornadiene (1) takes place with efficient kinetic resolution and gives an easily separable mixture of the corresponding (S,S)-bis-imine (3) and (R)-mono-imine (4). The absolute configuration of 3 has been established by X-ray crystal structure analysis. The coordination chemistry of enantiopure 3 with Pd(II), Rh(I), and Ru(II) has been investigated. The reaction of PdCl2(cod)] mainly affords a binuclear complex 6 whose structure has been established by X-ray analysis. One unit is coordinated to one P and one PdCl+ unit is tricoordinated to the other P and the two N. The two square planar units are parallel and the Pd?Pd distance is 3.1787(5) Å. The reaction of RhCl(cod)]2 gives the very reactive tetracoordinate cationic Rh(P2N2)]+ species 7 which is able to activate one C-Cl bond of chloroform to give the dichloromethyl-Rh complex (8) whose octahedral structure has been ascertained by X-ray analysis. |
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Keywords: | 1-phosphanorbornadienes Enantiopure P N ligands Kinetic resolution Pd Rh Ru complexes |
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