118681-53-1Relevant articles and documents
Nucleophilic properties and electrochemistry of five-coordinate rhodium(I) σ-cyanide complexes. Synthesis and characterization of stable cis hydride cyanide complexes of rhodium(III)
Bianchini, Claudio,Laschi, Franco,Ottaviani, M. Francesca,Peruzzini, Maurizio,Zanello, Piero,Zanobini, Fabrizio
, p. 893 - 899 (2008/10/08)
The trigonal-bipyramidal (TBP) σ-cyanide complexes of rhodium(I), [(L)Rh(CN)] [L = N(CH2CH2PPh2)3, 1; P(CH2CH2PPh2)3, 2], have been synthesized and spectroscopically characterized. The redox properties of both compounds have been studied in detail and compared with those of the σ-acetylide congeners [(L)Rh(C≡CR)] (R = Ph, CO2Et). One-electron oxidation of 1 and 2 yields the stable paramagnetic Rh(II) derivatives [(L)Rh(CN)]+ which exhibit square-pyramidal structures as determined by ESR spectroscopy. One-electron oxidation of the Rh(II) compounds gives unstable Rh(III) species of formula [(L)Rh(CN)]2+ which readily decompose to the dicyano complexes [(L)Rh(CN)2]+. Electrophilic attack by Me+ on 1 and 2 occurs at the nitrogen atom of the σ-bonded cyanide group to give the TBP methyl isocyanide complexes [(L)Rh(CNMe)]+. In contrast, protonation of 1 and 2 takes place at the metal, and the stable, octahedral cis hydride cyanide complexes [(L)Rh(H)(CN)]+ form.