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have a rigid structure even at 193 K. DFT calculations in model systems of 2, 3, and 4, in which the bulky ligands have been replaced by small models, followed by QM/MM optimizations with the real ligands have allowed the complete determination of the hydride positions and of the role played by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.
Synthesis and reactivity of β-stannylated phenylalanines
D?lling, Karin
, p. 3 - 16 (2017)
The free radical hydrostannation of a series of N-benzoyl and N-acetyl dehydrophenylalanine esters 2a-h yields β-stannylated phenylalanine derivatives 3 and 4. This addition of tin hydride to such unsaturated compounds simultaneously creates two new chiral centers leading to mixtures of two diastereomeric pairs of enantiomers. The reaction of 3-stannylated phenylalanine 3 with methanolic HCl yields chlorostannyl-substituted compounds 5 and 6 and, with one equivalent of bromine, the bromostannylated compounds 7 and 8 are formed. The bromostannylated phenylalanine derivative 7 reacts with one further equivalent of bromine to produce the dibromostannylated compound 9. Even the chlorostannylated phenylalanine derivative 5 reacts with one further equivalent of HCl to give the dichlorostannylated compound 10. The products were characterized by elemental analysis, infrared (IR), and multinuclear (1H, 13C, 119Sn) nuclear magnetic resonance (NMR) spectroscopy. Attempts were made to assign the preferred conformation of the stannylated phenylalanine derivatives using Karplus-type relationship of coupling constants 3J(H,H), 3J(Sn,H), and 3J(Sn,C=O). The results of these analyses have been confirmed by three crystal structure determinations.
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.
Tri- and diorganostannates containing 2-(N,N-dimethylaminomethyl)phenyl ligand
?vec, Petr,?erno?ková, Eva,Padělková, Zdeňka,R??i?ka, Ale,Hole?ek, Jaroslav
, p. 2475 - 2485 (2010/11/16)
The C,N-chelated tri and diorganotin(IV) chlorides react with both protic mineral acids and carboxylic acids. The nitrogen atom of the LCN ligand (where LCN is 2-(dimethylaminomethyl)phenyl) is thus quarternized - protonated and new Sn-X bond (X = Cl, Br, I or the remainder of the starting acid used) is simultaneously formed. The set of zwitterionic tri and diorganostannates containing protonated 2-(dimethylaminomethyl)phenyl-moiety was prepared and structurally characterized by multinuclear NMR spectroscopy and XRD techniques. In all these cases, the intramolecular N-H?X bond is present in the molecule. Despite the central tin atom remains five-coordinated (except for the [HLCNH]+[(n-Bu)2SnCl(NO 3)2]-) and reveals a distorted trigonal bipyramidal geometry, the 119Sn NMR chemical shift values of these zwitterionic stannates are somewhat shifted to the higher field than corresponding starting C,N-chelated tri and diorganotin(IV) halides. Reactions of C,N-chelated organotin(IV) halides with various Lewis acids are also discussed.
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.
Platinum-catalyzed phenyl and methyl group transfer from tin to iridium: Evidence for an autocatalytic reaction pathway with an unusual preference for methyl transfer
Smith, Stuart E.,Sasaki, Jennifer M.,Bergman, Robert G.,Mondloch, Joseph E.,Finke, Richard G.
, p. 1839 - 1841 (2008/09/17)
Platinum complexes have been found to catalyze the transfer of σ-bound ligands to the Ir center in Cp*(PMe3)IrCl2 (Cp* = η5-C5Me5) from Bu3SnPh and PhxSnMe
Alkali-metal sandwich complexes of a 1,2-diaza-3,5-diborolyl ligand featuring η1, η2, η3, and η4 coordination modes
Ly, Hanh V.,Forster, Taryn D.,Corrente, Andrea M.,Eisler, Dana J.,Konu, Jari,Parvez, Masood,Roesler, Roland
, p. 1750 - 1756 (2008/10/09)
The ring closure of 1,2-diisopropylhydrazine and 1,1-bis(phenylchloroboryl) ethane produced a heterocyclic compound with a CB2N2 framework. Deprotonation of this precursor yielded 1,2-diisopropyl-4-methyl-3,5- diphenyl-1,2-diaza-3,5-diborolyl, a cyclopentadienyl analogue containing only one carbon atom in the ring skeleton. Lithium, sodium, and potassium salts of the new ligand have been prepared and characterized. The structures of both monomeric and polymeric sodium metallocenes, as well as the structures of polymeric potassium metallocenes incorporating the new heterocycle, have been determined by single-crystal X-ray diffractometry. These structures reveal not only many similarities but also significant differences in the coordination behavior of the new ligand compared with that of the carbon-based analogue.
Mercapto derivatives of triorganotin Y,C,Y-pincer complexes: Role of Y,C,Y-chelating ligands in a new coordination mode of organotin compounds
Martincová, Jana,Dostál, Libor,Taraba, Jan,R??i?ka, Ale?,Jambor, Roman
, p. 3415 - 3423 (2008/02/12)
We report the use of triorganotin fragments R2L1-2Sn containing N,C,N and O,C,O-ligands L1-2(L1 = C6H3(Me2NCH2)2-2,6-, L2 = C6H3(tBuOCH2)2-2,6-) on stabilization of both thiol-form in R2L1-2Sn-2-SPy (2-SPy = pyridine-2-thiolate) and thione-form in R2L1-2Sn(mimt) (mimt = 1-methylimidazole-2-thiolate) of the polar groups. Treatment of ionic organotin compounds [Me2L1Sn]+[Cl]- (1) and [Ph2L2Sn]+[OTf]- (2) with appropriate sodium salts Na-2-SPy and Na(mimt) resulted in the isolation of Me2L1Sn-2-SPy (3), Ph2L2Sn-2-SPy (4), Me2L1Sn(mimt) (5), Ph2L2Sn(mimt) (6). While polar group 2-SPy exists in its thiol-tautomeric form in compounds 3 and 4, the second polar group (mimt) has been stabilized as the thione-tautomeric form by triorganotin fragments R2L1-2Sn in compounds 5 and 6. The products were characterized by 1H, 13C and 119Sn NMR and IR spectroscopy, ESI/MS, elemental analyses and structures of 3, 6 were determined by X-ray diffraction study. The reactivity of compound 4 containing non-coordinated nitrogen atom of 2-SPy polar group towards CuCl and AgNO3 is also reported. The reactions led to isolation of organotin compounds Ph2L2SnCl (7) and Ph2L2SnNO3 (8) as the result of polar group transfer. The mechanism of this reaction has been investigated and compounds Ph3Sn-2-SPy (9) and Ph2L2Sn-4-SPy (10) (4-SPy = pyridine-4-thiolate) have been prepared for this purpose.
Novel triphenyltin substituted derivatives of heavier alkaline earth metals
Englich, Ulrich,Ruhlandt-Senge, Karin,Uhlig, Frank
, p. 139 - 147 (2007/10/03)
The synthesis and characterization of a family of novel alkaline earth metal stannides, in addition to tri- and pentastannanes are described. [Ba(18-crown-6)(HMPA)2][SnPh3]2 (4), [Ca(18-crown-6)(HMPA)2][Sn(SnPh3)3]2 (5), and [Sr(18-crown-6)(HMPA)2][Sn(SnPh3)3]2 (6) were synthesized by insertion of the corresponding alkaline earth metals into the tin-tin bond of hexaphenyldistannane. Ph3SnSnPh2SnPh3 (7), and Sn(SnPh3)4 (8) became available by treating 4 with diphenyldichlorostannane. All compounds were studied by NMR spectroscopy, and X-ray crystallography. The stannanes 7 and 8 were also characterized by elemental analysis.
Intramolecular donor-assisted cyclization of organotin compounds
Mehring, Michael,L?w, Christian,Schürmann, Markus,Jurkschat, Klaus
, p. 887 - 898 (2007/10/03)
New intramolecularly coordinated organotin compounds containing the monoanionic O,C,O-coordinating ligand {4-tert-Bu-2,6- [P(O)(OEt)2]2C6H2}- have been synthesized by substitution reactions starting from organotin halides. In view of the enhanced reactivity of the intramolecularly coordinated compounds [4-tert-Bu-2,6- [P(O)(OEt)2]2C6H2}SnR2R' (2, R = Ph, R' = CH2SiMe3; 3, R = R' = Ph; 6, R = R' = Cl), cationic tin species are suggested to occur as intermediates in the formation of the heterocyclic compounds [1(Sn),3(P)Ph2SnOP(O)(OEt)-5- tert-Bu-7-P(O)(OEt)2]C6H2 (8), [l(Sn), 3(P)-Ph(Me3SiCH2)SnOP(O)(OEt)-5- tert-Bu-7-P(O) (OEt)2]C6H2 (15), and {[1(Sn),3(P)-Cl2SnOP(O)(OEt)-5- tert-Bu-7P(O)(OEt)]C6H2}'2 (16). The latter compounds are formed by intramolecular cyclizations of pentacoordinate cationic tin species under elimination of ethyl halide. Furthermore, the synthesis of [1(Sn),3(P)- Ph2SnOP(O)(OH)-5-tert-Bu-7-P(O)(OH)2]C6H2 (13) is described. Reaction of 8 with an excess of MesSiBr leads to the unexpected formation of {2[P(O)(OEt)(OSiMe3)]-4-tert-Bu-6-[P(O)(OEt)2]C6H2}SnPhBr2 (9) as a result of an O-Sn bond cleavage initiated by Me3SiBr and subsequent reaction of the intermediate with further Me3SiBr under Sn-C bond cleavage. The high donor capacity and the rigidity of the new ligand [4-tert-Bu- 2,6[P(O)(OEt)2]2C6H2}- are demonstrated by X-ray diffraction analyses of the tetraorganotin compound 2 and the monoorganotin trichloride 6. Furthermore, the molecular structures of the 2,3,1-oxaphosphastannoles 8 and 16 are discussed.
