Molecular Dynamics within Diorganotin Systems: Solution and Solid State Studies of New Mixed Distannoxane Dimers [(t)Bu(2)(Cl)SnOSn(Cl)R(2)](2).
Di-tert-butyltin oxide, ((t)Bu(2)SnO)(3), reacts with R(2)SnCl(2) to give mixed distannoxanes [(t)Bu(2)(Cl)SnOSn(Cl)R(2)](2) (1, R = Me; 2, R = Et; 3, R = (i)Pr; 4, (n)Bu) whereas di-tert-butyltin hydroxide chloride, [(t)Bu(2)Sn(OH)Cl](2), reacts with [(n)Bu(2)SnO](n) to give the chlorohydroxydistannoxane [(t)Bu(2)(OH)SnOSn(Cl)(n)Bu(2)](2), 5; the dimeric nature of these tetraorganodistannoxanes was confirmed by crystal structure determinations of 1 and 4. Although stable in the solid state, compounds 1-4 rearrange to give a number of distannoxanes in solution. Addition of R(2)SnCl(2) (R = Me, (i)Pr, (n)Bu) to solutions of 1, 3, and 4, respectively, causes displacement of (t)Bu(2)SnCl(2) with concomitant formation of [((t)Bu(2)SnCl(2))(R(2)SnO)(2)(R(2)SnCl(2))] and [(R(2)SnCl(2))(R(2)SnO)(2)(R(2)SnCl(2))]. Thus 1-4 can be regarded as (R(2)SnO)(2) units which are stabilized by two (t)Bu(2)SnCl(2) molecules. NMR data indicate that reaction between ((t)Bu(2)SnO)(3) and (t)Bu(2)SnCl(2) gives rise to an equilibrium involving linear [(t)Bu(2)Sn(Cl)OSn(Cl)(t)Bu(2)] and the novel three-quarter ladder compound [(t)Bu(2)SnCl(2)][(t)Bu(2)SnO](2). Formation of trinuclear tin species is also evident from electrospray mass spectrometric studies.
Dakternieks
Dainis
D
Department of Chemistry, University of Adelaide, Adelaide, South Australia 5005, Australia.
Jurkschat
Klaus
K
van Dreumel
Serena
S
Tiekink
Edward R. T.
ER