Issue 19, 2000

Proton addition and hydrogen-bond formation in reactions of the dicyano-complex [NBu4][trans-Re(CN)2(dppe)2] with protic reagents

Abstract

[NBu4][trans-Re(CN)2(dppe)2] (1, dppe = Ph2PCH2CH2PPh2) reacted with protic acids (HA = HBF4, CH3CO2H or [Et3NH][BPh4], added in stoichiometric amounts) to give, on protonation of one of the cyano-ligands, the isocyanide complex trans-[Re(CN)(CNH)(dppe)2] 3a, whereas the hydrogen-bonded cyano-adducts trans-[Re(CN·HO2CCF3)2(dppe)2] 4, trans-[Re(CN·HOMe)2(dppe)2] 5 and trans-[Re(CN·HNEt3)2(dppe)2][BPh4] 6 were obtained on treatment of 3a with an excess of CF3CO2H or of 1 with an excess of MeOH or [Et3NH][BPh4], respectively. However, solvent or other molecules can be trapped in the crystal lattice without hydrogen-bond interaction and trans-[Re(CN)2(dppe)2]·2L (L = MeOH 2a or Me2CO 2b) or trans-[Re(CN)2(dppe)2]·NEt37 are formed on attempted recrystallization of 1 from MeOH or Me2CO, or as a side product in the reaction of 1 with [Et3NH][BPh4], respectively. The crystal structures of 2b, 4, 5 and partially that of 2a were also determined and the anodic cyclic voltammetric behaviour (which is shown to distinguish between the CN–H and the hydrogen-bond CN  H formations) of the above complexes is described as well as an interpretative theoretical study (by extended Hückel and ab initio methods) of the CN and CNH complexes.

Supplementary files

Article information

Article type
Paper
Submitted
25 May 2000
Accepted
15 Aug 2000
First published
18 Sep 2000

J. Chem. Soc., Dalton Trans., 2000, 3393-3400

Proton addition and hydrogen-bond formation in reactions of the dicyano-complex [NBu4][trans-Re(CN)2(dppe)2] with protic reagents

M. F. N. N. Carvalho, A. M. Galvão and A. J. L. Pombeiro, J. Chem. Soc., Dalton Trans., 2000, 3393 DOI: 10.1039/B004189K

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