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

Abstract

Public reporting burden for tliis collection of information is estimated to average 1 hour per response, including ttie time for reviewing instructions, searching existing data sources, gathenng and maintaining the data needed, and completing and reviewing this collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing this burden to Department of Defense, Washington Headquarters Sen/ices, Directorate for Information , 1215 Jefferson Davis Highway Suite 1204, Arlington, VA 22202-4302. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to any penalty for failing to comply with a collectiori of information if it does not display a currently valid 0MB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. REPORT DATE (DD-MM-YYYY) 03-01-2003 REPORT TYPE Technical Paper TITLE AND SUBTITLE Methyl Tin(IV) Derivatives of HOTeFj and HN(S02CF3)2: A Solution Multi-NMR Study and X-ray Crystal Structures of (CH3)2SnCI(OTeF5) and (CH3)3Sn(H20)2]N(SO2CF3)2] AUTHOR(S)Ashwani Vij, William W. Wilson, Vandana Fook S. Tham Vij, Robert C. Corely' PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES)' SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES)Air Force Research Laboratory (AFMC) AFRL/PRS 5 Pollux Drive Edwards AFB CA 93524-7048 DISTRIBUTION / AVAILABILITY STATEMENTApproved for public release; distribution unUmited. SUPPLEMENTARY NOTES DATES COVERED (From -To AbstractThe new tin(IV) species, (CH3)2SnCl(OTeF5), was prepared via solvolysis of (CH3)3SnClin HOTeFs or from the reaction of (CH3)3SnCl with ClOTeFs 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 Pliln {a = 5.8204(8) A, b. NMR spectroscopy of (CH3)3SnX, prepared from excess Sn(CH3)4 and HX (X = OTeFs or N(S02CF3)2), revealed a tetracoordinate tin environment using (CH3)3SnX as a neat liquids or in CH2CI2 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-OTeFs bond is broken and the (CH3)3Sn(0=S(CH3)2)2'' cation and the OTeFs" are a convenient preparative route to the corresponding organotin(IV) derivatives. In these acidolysis reactions, Sn-Cl as well as Sn-C bond cleavage have been observed, with Sn-Cl bond cleavage being preferred. Alkyl tin(rV) derivatives of acids are commonly polymeric due to vacant coordination sites on tetracoordinate tin(IV). The bridging occurs through halogen atoms or the oxoacid ligands. In the solid state, the methyl tin halides, (CIl3)3SnF^'^ and (CH3)3SnCl^form extended halogen-bridged chains with pentacoordinate tin, while (CH3)2SnF2^ has a sheetlike polymeric structure with hexacoordinate tin. The crystal structures of (CH3)2Sn(S03F)2,^° (CH3)3SnOOCCF3," (C6Hi2)3SnOOCC3H7,'' and (CH3)2SnCl(OOCCH3)'...