X-ray Crystallographic and Mössbauer Spectroscopic Applications in Dependence of Partial Quadrupole Splitting, [R], on the C-Sn-C Angle in Seven-Coordinated Diorganotin(IV) Complexes

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• 作者：Gerimá ; rio F. de Sousa ; Victor M. Deflon ; Maria T. do P. Gambardella ; Regina H. P. Francisco ; Jos&eacute ; D. Ardisson ; and Elke Niquet
• 刊名：Inorganic Chemistry
• 出版年：2006
• 出版时间：May 29, 2006
• 年：2006
• 卷：45
• 期：11
• 页码：4518 - 4525
• 全文大小：183K
• 年卷期：v.45,no.11(May 29, 2006)
• ISSN：1520-510X

文摘

The synthesis and the IR, NMR (P>1H, ¹³C, and ¹¹⁹Sn), and Mössbauer spectroscopies and single-crystal X-raydiffraction studies of seven-coordinated diorganotin(IV) complexes, namely, [Ph₂Sn(Hdapsc)]Cl·H₂O·DMF [7; H₂dapsc = 2,6-diacetylpyridine bis(semicarbazone)], [Me₂Sn(H2,6Achexim)]Br·H₂O [8; H₂2,6Achexim = 2,6-diacetylpyridine bis(3-hexamethyleneiminylthiosemicarbazone)], [Me₂Sn(dapmts)] [9; H₂dapmts = 2,6-diacetylpyridinebis(4-methythiosemicarbazone)], and [ⁿBu₂Sn(dapmdtc)] [10; H₂dapmdtc = 2,6-diacetylpyridine bis(S-methydithiocarbazate)], were done. The determination of the structures of [Ph₂Sn(Hdapsc)]⁺, [Me₂Sn(H2,6Achexim)]⁺ and [Me₂Sn(dapmts)], [ⁿBu₂Sn(dapmdtc)] revealed the presence of monocationic and neutral complexes, respectively. Thestructures consist of monomeric units in which the Sn^IV ions exhibit distorted pentagonal-bipyramidal geometries,with the X,N,N,N,X-donor (X = O, S) systems of the ligands lying in the equatorial plane and the organic groupsin the apical positions. The C-Sn-C angle in the seven-coordinated diorganotin(IV) complexes was estimatedusing a correlation between Mössbauer and X-ray data based on the point-charge model and using new valuesobtained in this work for [alkyl] = -1.00 mm s^-1 and [aryl] = -0.80 mm s^-1 for complexes containing O,N,N,N,O-pentadentate ligands and new values for [alkyl] = -0.87 mm s^-1 and [aryl] = -0.75 mm s^-1 for complexescontaining S,N,N,N,S-pentadentate ligands.