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 [PdCl 2(cod)] mainly affords a binuclear complex 6 whose structure has been established by X-ray analysis. One PdCl 3 - 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(P 2N 2)] + 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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