88652-68-0Relevant articles and documents
Di-n-butyltin methyl- and phenylphosphonates
Ribot, Fran?ois,Sanchez, Clément,Biesemans, Monique,Mercier, Frédéric A. G.,Martins, José C.,Gielen, Marcel,Willem, Rudolph
, p. 2593 - 2603 (2001)
The structure of [Bu2Sn(HO3PMe)2]2 (1), as determined by single-crystal X-ray diffraction, is based on a dimer containing bridging and terminal hydrogenophosphonate ligands. The tin atoms are formally five-coordinate, but exhibit also two additional remote contacts, d(Sn-O) ≈ 3.14 ?, which results in a 5+2 type coordination. This crystalline compound and the three other amorphous compounds, Bu2Sn(O3PMe) (2), Bu2Sn(HO3PPh)2 (3), and Bu2Sn(O3PPh) (4), have been characterized by solid state 31P and 119Sn MAS NMR. Compound 1 exhibits a very well resolved 31P MAS NMR spectrum in which three different 2J-(31P-119/117Sn)iso scalar couplings can be measured. 31P and 119Sn NMR, 31P-19Sn HMQC spectroscopy, and various other 2D NMR techniques at variable temperatures were used to unravel the basic structural unit of compounds 2 and 4 in solution, which is proposed to be based on a trigonal bipyramid of the type R2SnO3 with two apical and one equatorial oxygen atom. Compound 1, in solution, displays a similar local geometry at tin and the same dimeric unit as in the crystalline state. In contrast with 2 and 4, however, compounds 1 and 3 display and extremely high degree of stereochemical fluxionality based on fast exchange of the bridging and terminal hydrogenophosphonate ligands.
Oxy- and Thio-phosphorus Acid Derivatives of Tin. Part 12. A Moessbauer Spectroscopic Investigation of the Structures and Polymorphic Behaviour of Diorganotin(IV) Phenyl-phosphonates and -arsonates
Cunningham, Desmond,Firtear, Padraig,Molloy, Kiaran C.,Zuckerman, Jerald J.
, p. 1523 - 1528 (2007/10/02)
The phenylphosphonate and phenylarsonates Me2Sn, Me2Sn, and Bun2Sn are isolated as their α-modifications from the reaction of dimethyl- or di-n-butyl-tin dichloride with the monosodium salt of the appropriate acid. β-Modifications are obtained by removal of water from the monohydrates Me2Sn*H2O, Me2Sn*H2O, and Bun2Sn*H2O, obtained in turn from the reaction of the diorganotin dichloride with the disodium salt of the appropriate acid.Only one form of Ph2Sn was isolated; this can be obtained either from the direct reaction of diphenyltin dichloride with phenylphosphonic acid or by removal of water from Ph2Sn*H2O.On the basis of i.r. and variable-temperature Moessbauer spectroscopic and X-ray powder diffraction data it is suggested that the structures of the β-modifications and of Ph2Sn consist of infinite chains, and that chains with similar backbone structures occur in solid-state forms of their hydrate precursors.The α-modifications of Me2Sn and Bu(n)2Sn appear to have two-dimensional sheet structures in which tin achieves five-co-ordination, but the data do not preclude the possibility that α-Me2Sn has a more associated three-dimensional network structure, with tin in highly distorted octahedral sites.The complexes Me2Sn2, Bun2Sn2, and Bun2Sn2, obtained by the reaction of a diorganotin dihalide with the appropriate acid, have structures in which tin is in octahedral sites.It is suggested that these are chain structures in which chains are linked by strong hydrogen bonds.