831193-36-3Relevant articles and documents
Synthesis and structures of β-diketiminatotin(II) halides, an amide and of Sn(=E)[{N(R)C(Ph)}2CH](NR2) (E = S or Se, R = SiMe3)
Hitchcock, Peter B.,Hu, Jin,Lappert, Michael F.,Severn, John R.
, p. 4193 - 4201 (2007/10/03)
Treatment of [Li(L1)]2 (1) or K(L2) (2) with SnX2 in Et2O yielded the heteroleptic β-diketiminatotin(II) halides Sn(L1)Cl (3a), Sn(L1)Br (3b) or Sn(L2)Cl (4), even when an excess of the alkali metal β-diketiminate was used [L1 = {N(R)C(Ph)}2CH, L 2 = {N(R)C(Ph)CHC(Bu1)N(R)}, R = SiMe3]. From 2 and half an equivalent each of SnCl2·2H2O and SnCl2, or one equivalent of SnCl2·2H2O, the product was Sn(L3)Cl (5) or Sn(L4)Cl (6), in which one or both of the N-R bonds of L1 had been hydrolytically cleaved; the compound Sn(L5)Cl (7) was similarly obtained from 1 and an equivalent portion of SnCl2·2H2O [L3 = {N(R)C(Ph)CHC(Bu1)N(H)}, L4 = {N(H)C(Ph)CHC-(Bu 1)N(H)} and L3 = {N(H)C(Ph)}2CH]. The halide exchange between 3a and 3b, studied by two-dimensional 119Sn{ 1H}-NMR spectroscopy, is attributed to implicate a (μ-Cl)μ-Br)-dimeric intermediate or transition state. The 13C{1H}-NMR spectra of 3a or 3b showed two distinct resonances for each group, which coalesced on heating, corresponding to ?G338 K = 69.4 (3a) or 72.8 (3b) kJ mol-1. The chloride ligand of 3a was readily displaced by treatment with NaNR2, CF3SO3H or CH2(COPh)2, yielding Sn(L1)X (X = NR2 (8), O1SCF3 (9) or {OC(Ph)}2CH (10)]. Oxidative addition of sulfur or selenium to 8 gave the tin(IV) terminal chalcogenidcs Sn(E)(L1)(NR2) [E = S (11) or Se (12)]. The X-ray structures of the cocrystal of 3a/3b and of the crystalline compounds 5, 6, 8, and 11 are presented, as well as multinuclear NMR spectra of each of the new compounds.
