Author: Rolfe H. Herber

Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si-Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles

The synthesis and spectroscopic and structural characterization of an extensive series of acyclic, monomeric tetrylene dichalcogenolates of formula M(ChAr)2 (M = Si, Ge, Sn, Pb; Ch = O, S, or Se; Ar = bulky m-terphenyl ligand, including two new acyclic silylenes) are described. They were found to possess several unusual features-the most notable of which is their strong tendency to display acute interligand, Ch-M-Ch, bond angles that are often well below 90°. Furthermore, and contrary to normal steric expectations, the interligand angles were found to become narrower as the size of the ligand was increased. Experimental and structural data in conjunction with high-level DFT calculations, in…

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Studies on adducts of organotin(IV) halides with bis(acetylacetone)ethylenediimine

The solid state configuration of 1/1 adducts, formed by mono-, di- and tri-organotin(IV) halides with the potentially tetradentate ligand bis(acetylacetone)ethylenediimine, has been investigated. The infrared spectra suggest that the neutral ligand coordinates SnIV through N (or O) atoms of the H-bonded acetylacetoneimine moieties. The skeletal vibrations associated to Sn-C and Sn-Cl bonds are consistent with square planar configurations of the organotin(IV) halide moieties, where SnCl3 and C3Sn groups would be T-shaped, and Alk2SnCl2 would have trans-dialkyl, trans-dichloro arrangements. The latter configuration is supported by the magnitude of the quadrupole splittings. Measurements of th…

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Organotin(IV) azido and mixed azidothiocyanato complex anions; A Mössbauer and vibrational spectroscopic study

Abstract Tetraphenylarsonium and tetramethylammonium salts of the complex anions Ph 3 Sn(N 3 ) − 2 , Ph 3 Sn(N 3 )(NCS) − , Me 2 Sn(N 3 ) 2− 4 and Ph 2 Sn(N 3 ) 2 (NCS) 2− 2 have been synthesized, and the solid state configuration of the complex anions has been studied by Mossbauer and vibrational spectroscopies. Trigonal bipyramidal structures are advanced for the Ph 3 Sn IV derivatives, with equatorial SnC 3 and apical pseudohalide ligands, while the R 2 Sn IV compounds are assumed to be trans -octahedral species. The NCS − ligands are observed to be N-bonded to Sn IV . Conductance and PMR (for the Me 2 Sn IV compound) data suggest the presence of the complex anions also in solution phase…

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Synthesis and structural studies by infrared and Mössbauer spectroscopy of adducts of tin(IV) and organotin(IV) derivatives with 2,2′-azopyridine

Abstract A number of complexes have been prepared by the reaction between 2,2′-azopyridine(AZP) and tin(IV) halides and organotin(IV) halides, and characterized by elemental analysis and infrared and variable temperature 119Sn Mossbauer spectroscopies. All of the new compounds have 1:1 stoichiometry, with the AZP ligand occupying two coordination sites by bonding through one of the ring and one of the azo group nitrogen atoms, to give rise to distorted octahedral structures. In the diorganotin complexes the two organic groups occupy trans positions. The infrared and Mossbauer spectroscopic data suggest that these compounds are monomeric in the solid state.

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