| Abstract
| - A synthesis towards cyclodistib(V)azane complexes has been developed by the reaction of organoantimony(V) chlorides with varying stoichiometric amounts of lithiated primary amines. These compounds have potential uses as ligands and possess reactive functionality which may make them versatile building blocks for more complex main group element architectures. An analysis of Sb−N bond lengths from the CSD shows that the precise bond length is influenced by a range of factors.
- High-yielding syntheses of complexes based around the cyclodistibazane (Sb2N2) core are described from thereaction of organoantimony(V) chlorides with varying stoichiometric amounts of lithiated primary amines, LiN(H)R.Thus, mixing Ph3SbCl2 with 2 equiv of LiN(H)R (R = CH2Ph) produces Ph3Sb(μ-NR)2SbPh3 (1). Mixed amido/imido complexes of formula {R(H)N}Ph2Sb(μ-NR)2SbPh2{N(H)R} (2) (R = CH2Ph, 2-OMe-5-tBu-C6H3, and Cy)are made from the corresponding 3:1 molar ratio combination of LiN(H)R with Ph2SbCl3. A similar reaction employingonly 2 equiv of LiN(H)R (R = CH2Ph) with 1 equiv of Ph2SbCl3 yields ClPh2Sb(μ-NR)2SbPh2Cl (3). Compounds2a−c and 3 possess reactive functionality which may make them useful synthetic reagents in the preparation ofmore complex main group imido architectures. All of the complexes have been characterized by 1H NMR spectroscopy,elemental analysis (CHN), and X-ray crystallography. An investigation of all known crystallographically characterizedSb−N fragments from the Cambridge Structural Database highlights a series of parameters that appear to influencethe observed Sb−N bond lengths.
|
