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Full crystal structures are reported for the tris(o-methoxyphenyl)tin compounds, (o-CH3OC6H4)3SnX [X=Cl (A), F (B)] and [(o-CH3OC6H4)3Sn]2O (C), together with both solid-state and solution (CDCl3) 119Sn NMR data for B and C as well as (Mes)3SnF and [(o-Tol)3Sn]2O. Compound B like A is monomeric with a similar but not identical arrangement of aryl groups around the tin while NMR data indicate that B has almost the same geometry in solution as in the solid state. The anomalously lower frequency δ(119Sn) value for B is consistent with the more ionic character of the SnF bond compared with other SnX (X=Cl, Br, I) bonds. Compound C is the first (Ar3Sn)2O with an SnOSn bond angle between 140 and 180°. The comparison of solid-state with solution 2J(119Sn,119Sn) values for C and [(o-Tol)3Sn]2O suggests that the solid state favours structures having larger SnOSn angles. Reacting C with water gives (o-CH3OC6H4)3SnOH only in solution, identified by its 13C and 119Sn NMR spectra.

Monomeric non-cyclic and dimeric cyclic bis(amino)stannylenes react with tin(IV) chloride to give the corresponding bis(amino)tin dichlorides ( 1, 2 ) in essentially quantitative yield. By monitoring the exchange reaction between tin(IV) chloride and tetrakis(diethylamino)tin using 119 Sn NMR at low temperature, two intermediates ( 4, 5 ) were identified as binuclear complexes in which the tin atoms are bridged by two amino groups and one chloro ligand. The equilibrated 1:1 reaction mixture finally contains mainly bis(diethylamino)tin dichloride ( 3 ). The reaction between N,N ′-di-tert-butyl-1,3-diaminopropane/triethylamine (1:2) and SnCl 4 affords the cyclic bis(amino)tin dichloride ( 6 ) via elimination of HCl. The compounds 1–6 were characterized in solution by 1 H, 13 C, 29 Si and 119 Sn NMR. The solid state 119 Sn CP/MAS NMR spectrum of compound 6 proves that its monomeric character is retained also in the crystalline state.

Twenty three tin(IV) tetrahalide adducts with various monodentate ligands, cis - and trans - L 2 ·SnX 4 , were studied by IR and Raman spectroscopy at room temperature and above. The observed SnX stretching frequencies as well as the structure, are correlated with the donor number of the ligands. In some cases the basicity or the bulkiness of the ligand are not the prevalent factors in determining the structure of the complex.

The reaction of caesium trichlorostannate(II) with 7,7,8,8-tetracyanoquinodimethane affords two products, the 1:1 adduct, CsSnCl3·TCNQ, and the complex SnCl2·(TCNQ)2· 1 2 thf, whilst with tetramethylammonium trichlorostannate, three complexes, Me4NSnCl3·TCNQ, Me4NSn(TCNQ)3, and (Me4NSnCl3)·TCNQ, have been isolated. Tin(IV) chloride reacts with Δ2,2′-bis(5-methyl-1,3-benzodithiolidene) and Δ2,2′-bis(1,3-diphenylinidazolidene) to afford complexes of composition, (SnCl4)3·(TTF)2·(C6H6) 3 2 and SnCl4·(TNFPh) 1 2 , respectively. The structures of the complexes are discussed on the basis of infrared and tin-119 Mossbauer data.

The reaction between SnCl 4 and R 3−n SiH n+1 (n = 0−2) have been investigated [R = CH 3 , CH = CH 2 , CH 2 CHCH 2 , CCH, CCCF 3 , C 5 H 5 , C 6 H 5 , or Si(CH 3 ) 3 ]; the reaction with silacyclopent-3-ene was also investigated. All the reactions led to monochlorination at silicon without breaking the SiC and/or SiSi bonds except in some allylsilanes, and spectroscopic parameters for the new compounds CH 2 CHCHCH 2 Si HCl, CHCSiH 2 Cl, CF 3 CCSiH 2 Cl, (CH 3 ) 3 SiSiH 2 Cl, and (CH 3 ) 3 SiSiHCl 2 , all prepared by this route, are reported. For the disilanes, 29 Si and 13 C chemical shifts were measured by heteronuclear double resonance.