286386-36-5Relevant academic research and scientific papers
Oxidative addition to M(n) (M = Ge, Sn) amidinate complexes: Routes to group 14 chalcogenolates with hypervalent coordination environments
Foley, Stephen R.,Yap, Glenn P. A.,Richeson, Darrin S.
, p. 1663 - 1668 (2007/10/03)
Oxidative addition of diphenyl dichalcogenides, PhE-EPh (E = S, Se) to Ge(n) and Sn(n) amidinate complexes is reported. In the case of the bis(alkylamidinato)Ge complexes, Ge(CyNC(R')NCy) (Cy = cyclohexyl; R' = Me, 'Bu), six coordinate Ge(iv) compounds were isolated and the structure of (PhS)2Ge(CyNC(Me)NCy) (10) was confirmed by single crystal X-ray diffraction analysis. Mixed amidinato-amido species, M(CyNC(R')NCy)[N(SiMe3)2] (M = Ge, Sn; R = Me, 'Bu), react in a similar manner to yield novel bis(phenylchalcogenolate) complexes of Sn and Ge. Spectroscopic features and, in the case of (PhSe)2Ge(CyNC(Me)NCy)[N(SiMe3)2] (13), a single crystal structural analysis indicate that this ligand environment appears to favor Ge(iv) complexes with a strong disposition towards a tetrahedral geometry. In these cases, a five coordinate environment for the metal center is avoided by one of the amidinate ligands exhibiting a monodentate coordination mode, which preserves the pseudo-tetrahedral metal coordination geometry. These observations contrast with the Sn(n/iv) analogues which exhibit no such tendency. For example the single crystal structure of (PhS)2Sn(CyNC(Me)NCy)[N(SiMe3)2] (14) displays a bidentate ligand and a five coordinate metal coordination geometry. Complex 13 reacts with elemental Se to generate the terminal germanium selenide and regenerate PhSeSePh. Concomitant with this reaction is a rearrangement of the previously monodentate amidinate ligand to a bidentate coordination mode. The Royal Society of Chemistry 2000.
