Methyl Tin(IV) Derivatives of HOTeF5 and HN(SO2CF3)2: A Solution Multi- NMR Study and X-ray Crystal Structures of (CH3)2SnC1(OTeF5) and (CH3)3Sn(H2O) 2N(SO2CF3)2

摘要

The new tin(IV) species, (CH3)2SnCl(OTeF5), was prepared via solvolysis of (CH3)3SnCl in HOTeF5 or from the reaction of (CH3)3SnCl with ClOTeF5 and was characterized by NMR and vibrational spectroscopy, mass spectrometry, and single crystal X-ray diffraction. (CH3)2SnCl(OTeF5) crystallizes in the monoclinic space group P2(sub 1)/n (a = 5.8204(8) A, b =10. 782(1) A, c =15.493(2) A, beta=91.958(2), V =971.7(2) A (exp 3), Z = 4). NMR spectroscopy of (CH3)3SnX, prepared from excess Sn(CH3)4 and HX (X = OTeF5 or N(SO2CF3)2), revealed a tetracoordinate tin environment using (CH3)3SnX as a neat liquids or in CH2Cl2 solutions In acetone and CH3CN solution, the tin atom in (CH3)3SnOTeF5 was found to extend its coordination number to five by adding one solvent molecule. In the strong donor solvent, DMSO, the Sn-OTeF5 bond is broken and the (CH3)3Sn(O=S(CH3)2)2+ cation and the OTeF5(-) anion are formed. (CH3)3SnOTeF5 and (CH3)3SnN(SO2CF3)2 show different reactivity with water. While the OTeF5 group of (CH3)3SnOTeF5 undergoes complete hydrolysis, (CH3) 3SnN(SO2CF3)2 forms the stable hydrate salt, (CH3)3Sn(H2O)2N(SO2CF3)2. This salt crystallizes in the monoclinic space group P2(sub 1)/c (a = 7.3072(1) angstroms, b =13.4649(2) A, c =16.8(question mark)1(2) A, beta= 98.705(1)', V =1636.00(3) A(exp 3), Z = 4) and was also characterized by NMR and vibrational spectroscopy.