Synthesis and structure of cyclopentadienyl Tin(II) compounds /

Abstract

The boron trifluoride adduct of stannocene was reacted with the molybdenum hydride, HMo(CO)(, 3)((eta)('5)-C(, 5)H(, 5)). The compound was characterized by microanalytical analysis, melting point, NMR, ir, Mossbauer and mass spectroscopy. A crystal was grown from solutions of THF and acetone-ethanol, but the x-ray data could not be solved. The tin(IV) hydride, HSn{Mo(CO)(, 3)-(eta)('5)-C(, 5)(CH(, 3))(, 5)}(, 3), was synthesized and characterized.

A new class of divalent tin compounds, stannocenophanes, having the general formula C(, 6)H(, 4)(CH(, 2)C(, 5)H(, 4))(, 2)Sn, were prepared from the ortho-, meta- and para-isomers of the disodium salts of phenylenemethylenedicyclopentadienide and tin(II) chloride. The boron trifluoride adduct of the meta-isomer was synthesized and characterized.

A second new class of divalent organotin compounds was produced by the reaction of cyclopentadienyltin(II) chloride with the ring-substituted sodium salts NaC(, 5)H(, 4)R, where R = C(O)CH(, 3), C(O)OCH(, 3), C(O)OCH(, 2)CH(, 3). The products are the first examples of ring-substituted stannocenes.

The boron trifluoride adduct of stannocene was prepared and its single crystal x-ray structure solved at 138 K. The complex is described by the formula BF(, 4(.))((eta)('5)-C(, 5)H(, 5))(, 3)Sn(, 2(.))C(, 4)H(, 8)O. The complex crystallizes in the orthorhombic space group P2(, 1)2(, 1)2(, 1). Individual BF(, 4)('-), ((eta)('5)-C(, 5)H(, 5))(, 2)Sn, (eta)('5)-C(, 5)H(, 5)Sn('+) and THF units are linked together in a three-dimensional lattice.

The reaction of tin(II) chloride with thallium(I) cyclopentadienyl salts, TlC(, 5)H(, 4)X, where X = Cl, Br, I produces a mixture of products instead of the desired Sn((eta)('5)-C(, 5)H(, 4)X)(, 2). In the attempt to produce trimethyltin(IV) chlorocyclopentadiene from trimethyltin(IV) chloride and chlorocyclopentadienylthallium(I), the known compound N-trimethyltin(IV) succinimide was synthesized. Thallium(I) succinimide was produced in the synthesis of chlorocyclopentadienylthallium(I).

The synthesis of novel organotin(II) compounds was carried out in an attempt to understand the physical and chemical properties in these very reactive systems. Compounds comprising two new classes of organotin(II) complexes were prepared. Two single crystal x-ray data sets were collected with one successfully solved.