215233-67-3Relevant academic research and scientific papers
Heterocyclic systems containing antimony (III) -VIII . Hypervalency by intramolecular 1,5-chelation Sb · · · N in rings RSb [ (CH2) 3] 2NR′ (NR′ = NMe, NBz, NBui) and comparison to analogous compounds of AsIII, BiIII, GeIV and SnIV
Braeu, Elmar,Zickgraf, Andrea,Draeger, Martin,Mocellin, Enrico,Maeda, Masaki,Takahashi, Masashi,Takeda, Masuo,Mealli, Carlo
, p. 2655 - 2668 (1998)
Eleven antimony compounds RSb [ (CH2) 3] 2 NR′ and eight germanium compounds R2Ge [ (CH2) 3] 2 NR′ (some combinations of R = Cl, I, NCS, OSiPh3, Ph, and NR′ = NMe, NBz, NBui) have been synthesized by diGrignard reactions and subsequent treatment with AgSCN, Ph3SiONa or PhLi. The compounds were compared to 14 Sn, 1 As, 5 Sb and 4 Bi analogues taken from the literature. Evidence is provided for 1,5-chelation Sb · · · N via crystal structure determinations (5+1 (lit) Sb compounds) , 13C- and 29Si-NMR chemical shifts, 12;Sb and 12;I Moessbauer data (11 and 3 Sb compounds, respectively) , cyclic voltammetry (9 Sb compounds) and semi-empirical MO calculations on the Extended Hueckel level (8 present compounds and 4 models) . The ligand sequence (Cl i a decrease of the absolute value of the 12;Sb quadrupole coupling constant from Moessbauer spectroscopy occurs. The postulation of a control of the Sb · · · N chelation by frontier orbital interactions is supported by the CV results in CH2Cl2 at a AuHg electrode. It is proved by scan rate dependence that the observed reversible reductionoxidation process is diffusion controlled, and by coulometry that the reduction takes place by transfer of one electron.
