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. Tin metal reacts with 2,2'-dithiobis (pyridine) in refluxing toluene to give the pyridine-2-thiolate complex Sn(C5H4NS)4, l a . Multinuclear ( 7 7~e , '''sn) magnetic resonance shows that ligand redistribution occurs in l~: s n ( E P h )~ (E = S or Se) mixtures to give Sn(EPh)4-,(C5H4NS)x. From the pattern of the "'~n chemical shifts of these series, compared with that of Sn(EPh),-,(SR), (R = simple alkyl or aryl group), the complexes are shown to be five-coordinate Sn(EPh)3(C5H4NS-N,S) when x = 1 and six-coordinate Sn(EPh)4-x(C4H4NS-S)x-2(C5H4NS-N,S)2 when x = 2-4. Reaction of Sn(SPh)' and (C5H&!S)2 yields pure Sn(SPh)2(C5H4NS)2. The 13C NMR spectrum of Sn(C5H4NS-S)2 (C5H4NS-N,S)' is an exchange average down to 178 K, probably as a result of fluxionality. The series Sn(EPh)4-x(L')x (E = Se, L' = 5-nitropyridine-or quinoline-2-thiolate, x = 0-4; E = S or Se, L' = pyridine-2-thiolate-N-oxide, x = 0-2) can beprepared insitu by redox between Sn(EPh)4 and the disulfide (L1)'. Treatment of l a with X2 (X = Br or E-gives SnX4-,(C5H4NS-N,S), (x = 2 or 3), which have been characterized by NMR, and provides a new synthesis of the known dihalo complexes.In a recrystallization of l a from CH2C12:hexane Sn(C5H4NS)4.CsH5NS, 2, was obtained, probably as a result of hydrolysis. The structure of 2 has been solved by single crystal X-ray diffraction techniques. The compound crystallizes in the orthorhombic space group Pbca (No. 61) with a unit cell of dimensions a = 17.132 (2) L'Ctain mitallique rCagit avec la 2,2'-dithiobis (pyridine), dans le tolukne au reflux, pour donner le complexe pyridine-2-thiolate, Sn(C5H4NS)4, l a . La rtsonance magnktique multi-noyaux ( 7 7~e , "'~n) dCmontre que, dans des mClanges de l a : Sn(EPh)4 oh E = S ou Se, il se produit une redistribution des ligands et la formation de composts du type Sn(EPh)4-,(C5H4NS)x. En se basant sur une comparaison des dtplacements chimiques du "' Sn dans les composCs de cette strie avec ceux obsewks dans les produits Sn(EPh),-,(SR), ou R = groupements aryles ou alkyles simples, on a dCmontrC que, si x = I, les complexes sont les entitCs penta-coordonnCes Sn(EPh)3(C5H4NS-N,S) alors que, si x = 2-4, les complexes sont les entitks hexa-coordonn6es Sn(EPh)4-X(C5H4NS-S)2. La reaction du Sn(SPh)' avec le (C5H$JS)2 fournit du Sn(SPh)2(C5HflS)2 a 1'Ctat pur. M&me lorsqu'on abaisse la tempkrature jusqu'i 178 K, le spectre rmn du 13C du Sn(C5H4NS-S)2(C5H4NS-N,S)2 est un spectre moyen rCsultant probablement d'un mtcanisme de fluxion. Faisant appel a une rCaction redox in situ entre l e Sn(EPh)4, et le disulfure (L1)', on peut prCparer les produits de la sCrie Sn(EPh)4-,(L')x (E = Se, L' = 5-nitropyridine-ou quinolkine-2-thiolate, x = 0-4; E = S ou Se, ' L' = pyridine-2-thiolate N-oxyde, x = 0-2). Le traitement du produit l a par du X2 (X = Br ou I) fournit les complexes SnX4-,(C5H4NS-N,S), (x = 2 ou 3) que I'on a caractCrists par rmn; ces rkactions fournissent une nouvelle synthkse de ces complexes dihalogCnCs connus.Lors de la recristallisation du produit l a dans un mClange...

Stannane or the methylstannanes SnMeaPnHn ( n = 1-4) react i n fluorosulphuric acid at low temperature (-90 "C) to produce SnMeSnH,+ ( n = 0-3) and 'H, 13C, and I19Sn n.m.r. spectroscopy have been used in their characterisation. Hydrogen-evolution, I19Sn n.m.r., and Mossbauer evidence is presented t o show that at higher temperatures these species decompose t o Sn2+, Sn2+ plus SnMeZ2+, and SnMe22+ depending o n the starting hydride.Stannane and the methylstannanes have been well studied by a variety of spectroscopic techniques. Flitcroft and Kaesz ' reported n.m.r. data, and a correlation between J(' 19Sn-'H) and the tin-hydrogen stretching frequency v(Sn-H) has been made.* Tin-119 Mossbauer spectra of stannane and some organotin hydrides have been recorded., May and Spijkerman correlated Mossbauer and n.m.r. parameters for the methyltin hydrides.Sawyer and co-workers 5-7 have studied the reactions of organotin hydrides with acids. Di-n-butyltin dihydride reacts with HCI in dioxane to produce di-n-butyltin chloride hydride, with the evolution of 1 rnol of H,. This tin chloride hydride reacts further with an excess of acid to form SnBu",CI, and a further rnol of H,. An exchange reaction between SnBu",CI, and SnBu",H, gives SnBu",CIH.* Stannane reacts with strong acids, under controlled conditions, and Webster and Jolly have shown that SnH,' is produced. They showed that SnH, reacted slowly with strong aqueous acids, at low temperature, to produce 1 rnol of H, for every rnol of SnH,. On warming to room temperature a further 2 rnol of H, were produced. In HS0,F solution, at -78 "C, SnH, reacted rapidly to produce SnH,' and 1 rnol of H,. However, on warming to room temperature, no further H, was evolved. Birchall and Pereira l o have compared 'J(Sn-H) for the series SnH,', SnH,, and SnH,-.Similar behaviour is observed for SnMe, in HSO,F, when solvated SnMe,' and SnMe," are produced together with the evolution of CH,.' ' To our knowledge no one has studied the solvolysis of the methyltin hydrides in strong acids. In this paper we report our results on such reactions and provide n.m.r. spectroscopic evidence for the SnMe,', SnMe,H', SnMeH,+, and SnH,' cationic species in solution and evidence for the decomposition process.

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Spin-spin coupling is observed between 119Snli and 19F (1 128-635 Hz), and 119Snii and 119Sn1V (265-326 Hz) in compounds produced by the reaction of SnF2 with Sn(O2CRI4; the X-ray crystal structure of Snii2SniV-2F4(02CCF3)8-2CF3COOH has been determined.