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1,2-bis(organostannyl)ethanes as powerful bidentate Lewis acids. Crystal structures of (Ph2ClSnCH2)2 · (Me2N)2PO and [Ph3PNPPh3][(Ph2ClSnCH2)2 · Cl]

1990; Elsevier BV; Volume: 388; Issue: 3 Linguagem: Inglês

10.1016/0022-328x(90)85373-7

1872-8561

Klaus Jurkschat, Frank Hesselbarth, M. Dargatz, J. Lehmann, E. Kleinpeter, A. Tzschach, J. Meunier‐Piret,

Synthesis and characterization of novel inorganic/organometallic compounds

The synthesis of bis(organostannyl)ethanes of the types (Ph2XSnCH2)2 (1, X = Ph; 2, X = Cl; 3, X = Br; 4, X = I) and (Ph2XSnCH2)2 (5, X = Br, 6, X = I) is described. The compounds have been investigated by means of 1H, 13C and 119Sn NMR spectroscopy. 2 reacts with HMPA, [Ph3P = N = PPh3]+ Cl−, and Ph4PBr, respectively, to give the 1/1 complexes (Ph2ClSnCH2)2 · HMPA (7), [Ph2ClSnCH2)2 · Cl]−[Ph3PNPPh3]+ (8), and [(Ph2ClSnCH2)2 · Br]−[Ph4P]+ (9). The formation constant Ka for 8 in CDCl3 solution is 2260 M−1. The structures of 7 and 8 have been determined by X-ray diffraction. That of 7 shows that the two tin atoms are pentacoordinate but are inequivalent as a result of having different coordination sphere; one tin atom is coordinated by the monodentate HMPA (SnO 2.255(3) Å) whereas the other interacts with a bridging Cl (Sn(1); Cl(2) 3.000(1) Å). In the anion of 8, the bis(chlorodiphenylstannyl)ethane may be regarded as an unsymmetrical chelate ligand towards Cl(12) (Sn(1)-Cl(12) 2.83(1), Sn(2)-Cl(12) 2.70(1) Å).