639-58-7Relevant articles and documents
Preparation and characterization of osmium-stannyl polyhydrides: d4-d2 oxidative addition of neutral molecules in a late transition metal
Esteruelas, Miguel A.,Lledos, Agusti,Maseras, Feliu,Olivan, Montserrat,Onate, Enrique,Tajada, Maria A.,Tomas, Jaume
, p. 2087 - 2096 (2003)
Complex OsH2Cl2 (PiPr3)2 (1) reacts with 2.0 equiv of HSnPh3 to give the tetrahydridestannyl derivative OsH4Cl(SnPh3)(PiPr3)2 (2) and ClSnPh3. The structure of 2 has been determined by X-ray diffraction analysis. In the solid state and in solution at temperatures lower than 298 K, the coordination geometry around the osmium atom can be rationalized as derived from a distorted dodecahedron. In the presence of diphenylacetylene, complex 2 gives OsH3(SnClPh2){η2- CH2=C(CH3)PiPr2}(Pi Pr3) (3), cis-stilbene, and benzene. In the solid state, the structure of 3 determined by X-ray diffraction analysis can be described as a very distorted pentagonal bipyramid, with the phosphorus atom of the triisopropylphosphine ligand and the midpoint of the olefinic bond of the isopropenyl group of the dehydrogenated phosphine occupying axial positions. In solution, at temperatures higher than 233 K, the coordinated olefin is released. Complex 3 reacts with molecular hydrogen to afford the pentahydride OsH5(SnClPh2)(PiPr3)2 (4), as a result of the hydrogenation of the coordinated olefinic bond and the d4-d2 oxidative addition of hydrogen. The structure of 4 in the solid state also has been determined by X-ray diffraction. The coordination geometry around the osmium atom can be rationalized as a distorted dodecahedron. In solution, complex 4 does not have a rigid structure even at 193 K. DFT calculations in model systems of 2, 3, and 4, in which the bulky ligands have been replaced by small models, followed by QM/MM optimizations with the real ligands have allowed the complete determination of the hydride positions and of the role played by steric effects in the experimental structures.
Lorenz,Becker
, p. 3370 (1962)
Lewis
, p. 366,367 (1954)
Cristol,S.J. et al.
, p. 4007 - 4008 (1965)
A utility for organoleads: Selective alkyl and aryl group transfer to tin
Arias-Ugarte, Renzo N.,Pannell, Keith H.
, p. 1703 - 1708 (2018/02/09)
Me4Pb and Ph4Pb readily transfer methyl or phenyl groups to an equivalent molar ratio of tin(iv) chlorides in the order SnCl4 > MeSnCl3 > Me2SnCl2 > Me3SnCl, often in a selective manner. Me3PbCl and Ph3PbCl specifically transfer a single methyl/phenyl group under the same reaction conditions to produce recovered yields in >75%. Specific transfer of 2 methyl groups from PbMe4 can be achieved at elevated temperatures and/or a 2:1 molar ratio Pb:Sn.
Synthesis and characterization of some organotin(IV) adducts containing a related series of pyridines: Crystal structure of [SnMe2Cl2(bu2bpy)]
Momeni, Badri Z.,Shahbazi, Soheila,Khavasi, Hamid Reza
, p. 1393 - 1398 (2010/05/01)
Organotin(IV) complexes of [SnR(4-n)Cln] (n = 2, R = Me, nBu; n = 1, R = Ph) react with the bidentate pyridyl ligand 4,4′-di-tert-butyl-2,2′-bipyridine (bu2bpy) to give hexa-coordinated adducts with the general formula [SnR(4-n)Cln(bu2b py)]. However, the reaction of these organotin(IV) complexes with the corresponding monodentate ligand 4-tert-butylpyridine (bupy) resulted in the formation of the hexa-coordinated complex [SnMe2Cl2(bupy)2] and the penta-coordinated complexes [SnR(4-n)Cln(bupy)] (n = 2, R = nBu; n = 1, R = Ph). Moreover, the reaction of the above organotin(IV) complexes with 4,4′-trimethylenedipyridine (tmdp) yields hexa-coordinated adducts with the general formula [SnR2Cl2(tmdp)] (R = Me, nBu) and the penta-coordinated complex [ClPh3Sn-μ-(tmdp)SnPh3Cl] in the solid state. The resulting complexes have been characterized by multinuclear NMR (1H, 13C, 119Sn) spectroscopy and elemental analysis. NMR data shows that the triphenyltin(IV) adducts are not stable in solution and dissociate to give tetra-coordinated tin(IV) complexes. The X-ray crystal structure determination of [SnMe2Cl2(bu2bpy)] reveals that the tin atom is hexa-coordinated in an octahedral geometry with a trans-[SnMe2] configuration.
