Reactions of dimethyl- and diphenyl-mercury with dihalobis(isocyanide)palladium(II) complexes |
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| Authors: | B Crociani M Nicolini RL Richards |
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| Institution: | Centro di Chimica Tecnolgia Composti Metallorganici Elementi Transizione, C.N.R., Venezia Italy;Istituto di Chimica Generale dell''Universita, Padova Italy;School of Molecular Sciences, University of Sussex, Brighton BN9 1QJ Great Britain |
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| Abstract: | The reaction of cis-PdCl2(CNR)2] (R = Ph, p-MeC6H4, p-MeOC6H4) and trans-PdI2(CNPh)2] with HgR′2 (R′ = Me, Ph) followed by addition of PPh3 (Pd/PPh3, ) gives complexes of the type trans- PdX {C(=NR)C(R′)=NR}(PPh3)2] (X = Cl, I) I as main products. These bis(imino) compounds may result from double insertion of the coordinated isocyanides into a PdR′ σ-bond. NaBPh4 was also found to act like HgPh2 as a good phenylating agent towards coordinated isocyanide. The reactions of I with methanolic HClO4 yield cationic compounds: trans- PdX{C(NHR)C(R′)=NR}(PPh3)2]ClO4; the protonated bis(imino) group may also be formulated as {C(=NR)C(R′)NHR} and a fast equilibrium between the two forms probably exists in solution. The factors influencing the reaction with HgR′2 and spectroscopic data (IR and 1H NMR) for the complexes are reported and discussed. |
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| Keywords: | To whom correspondence should be addressed |
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