Synthesis and Structure of (N ,)C ,N -chelated Organoantimony(III) and Bismuth(III) Cations and Isolation of Their Adducts with Ag[CB11 H12 ]

The treatment of N,C,N-chelated antimony(III) and bismuth(III) chlorides [C6H3-2,6-(CH=NR)2]MCl2 [R = tBu and M = Sb (1) or Bi (2); R = Dmp and M = Sb (3) or Bi (4)] (Dmp = 2,6-Me2C6H3) with one molar equivalent of Ag[CB11H12] led to a smooth formation of corresponding ionic pairs {[C6H3-2,6-(CH=NR)2]MCl}+[CB11H12]– [R = tBu and M = Sb (7) or Bi (8), R = Dmp and M = Sb (9) or Bi (10)]. Similarly, the reaction of C,N-chelated analogues [C6H2-2-(CH=NDip)-4,6-(tBu)2]MCl2 [M = Sb (5) or Bi (6), Dip = 2′,6′-iPr2C6H3] gave compounds {[C6H2-2-(CH=NDip)-4,6-(tBu)2]MCl}+[CB11H12]– [M = Sb (11) or Bi (12)]. All compounds 7–12 were characterized with 1H, 11B and 13C{1H} NMR spectroscopy, ESI-mass spectrometry, IR spectroscopy, and molecular structures of 7–9 and 12 were determined by the help of single-crystal X-ray diffraction analysis. In contrast, all attempts to cleave also the second M–Cl bond in 7–12 using another molar equivalent Ag[CB11H12] remained unsuccessful. Nevertheless, the reaction between 7 (or 8) and Ag[CB11H12] produced unprecedented adducts of both reagents namely {[C6H3-2,6-(CH=NtBu)2]SbCl}22+[Ag2(CB11H12)4]2– (13) and {[C6H3-2,6-(CH=NtBu)2]BiCl}+[Ag(CB11H12)2]– (14) in a reproducible manner. The molecular structures of these sparingly soluble compounds were determined by single-crystal X-ray diffraction analysis.