118681-54-2Relevant academic research and scientific papers
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.
Syntheses and characterization of trigonal-bipyramidal rhodium(I) complexes of tris(2-(diphenylphosphino)ethyl)phosphine and determination of a spectroscopic trans-influence series by 31P{1H} NMR spectroscopy
Gambaro, Jeffrey J.,Hohman, William H.,Meek, Devon W.
, p. 4154 - 4159 (2008/10/08)
A series of low-spin, five-coordinate rhodium(I) complexes of the tripod ligand tris(2-(diphenylphosphino)ethyl)phosphine, PP3, were synthesized and characterized by elemental analyses, infrared spectra, and 31P{1H} NMR spectra. The complexes have trigonal-bipyramidal geometries in which the PP3 ligand occupies four of the five sites of C3v symmetry and the variable fifth ligand is monodentate. The 31P NMR spectral patterns are consistent with AMX3 and AKMX3 spin systems. The NMR spectra permit a determination of the trans influence of the fifth ligand on the rhodium-phosphorus apical coupling constant and the chemical shifts of the apical and equatorial phosphorus atoms of PP3.
