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Redox behaviour and reactions of (PhCH2)3Sb; syntheses and structures of [(PhCH2)3SbMe]I and [(PhCH2)3SbMe]3Sb3I12

Authors
Journal
Journal of Organometallic Chemistry
0022-328X
Publisher
Elsevier
Publication Date
Volume
483
Identifiers
DOI: 10.1016/0022-328x(94)87160-4
Keywords
  • Antimony
  • Alkyl Complexes
  • X-Ray Structural Analysis
Disciplines
  • Chemistry
  • Communication

Abstract

Abstract (PhCH 2) 3Sb ( 1) reacts with MeI to form [(PhCH 2) 3SbMe]I ( 2). The action of excess I 2 on 2 gives [(PhCH 2) 3SbMe] 3Sb 3I 12 ( 3). 3 is synthesized in 78% yield by addition of SbI 3 to 2. The crystal structures of 2 and 3 are reported. The cations of 2 have a distorted tetrahedral coordination at Sb with SbC bond distances of 210.5(20)–215.7(20) pm and SbC 2 angles between 103.1° and 121.7°. Sb ⋯ I contacts of 373.3 pm increase the coordination at Sb to distorted trigonal bipyramids with Me and I in the axial positions. The crystals of 3 contain distorted tetrahedral [(PhCH 2) 3SbMe] + cations and (Sb 3I 12) 3− anions with the approximate structure of two SbI 3 molecules (mean SbI bond distances 283.2 pm) capping opposite planes of a SbI 3− 6 octahedron (mean SbI distance 302.4 pm). In addition to the preparative results the electrochemical properties of 1 are communicated and discussed.

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