962-89-0Relevant academic research and scientific papers
Transmetalation reactions yield new tetra- and pentairidium carbonyl complexes containing σ-bonded phenyl rings
Adams, Richard D.,Chen, Mingwei
, p. 5867 - 5872 (2012/01/03)
The new air-stable σ-phenyl tetrairidium carbonyl salt [Et 4N][Ir4(CO)11Ph], 1, has been obtained by transmetalation reactions between [Et4N][Ir4(CO)11Br] and SnPh3OH in 45% yield or SnPh4 in 36% yield. Compound 1 reacts with PPh3 to yield the complex [Et4N][Ir 4(CO)11(PPh2C6H4)], 2, which contains an ortho-metalated bridging PPh2C6H4 ligand across an edge of a tetrahedral cluster of four iridium atoms. Compound 2 reacts with Ir(CO)(PPh3)2Cl by halide displacement to yield the two new uncharged pentairidium complexes Ir5(CO)12(Ph) (PPh3), 3, and Ir5(CO)11(PPh 3)(PPh2C6H4), 4. Compounds 3 and 4 both contain trigonal-bipyramidal clusters of iridium atoms. Compound 3 contains a σ-phenyl ligand coordinated to one of the apical iridium atoms. Compound 4 contains an ortho-metalated PPh2C6H4 ligand that bridges an apical-equatorial edge of the trigonal-pyramidal cluster of metal atoms. Compound 4 was also obtained from 3 by reaction with PPh 3.
Easy general method for interhalide conversions in organotin compounds
Zobel, Bernhard,Lim, Allan E. K.,Dunn, Kerri,Dakternieks, Dainis
, p. 4889 - 4890 (2008/10/08)
The halides in organotin halides are easily interconverted in excellent yields using aqueous ammonium halide solutions and various organic solvents.
Cleavage Reactions of some Phenyltin Compounds with Iodine Halides, -Pseudohalides and -Carboxylates
Srivastava,Singh,Tangri,Sinha,Bajpai
, p. 443 - 445 (2007/10/03)
Cleavage reactions of iodinehalides, -pseudohalides IX (X = Cl, Br, NCO, NCS, N3 and CN) with Ph3SnCp yield triphenyltinhalides, -pseudohalides (Ph3SnX) indicating cleavage of Cp-Sn bond in preference to Ph-Sn bond, and cleavage reactions of iodine carboxylates IX′ (X′ = CH3OCO, C5H5OCO, C6H5CH2OCO, o-NH2C6H4OCO, o-CIC6H4OCO, p-NO2C6H4OCO, p-NH2C6H4OCO, C6H5CH =CHOCO) (in situ) with Ph3SnCl give hitherto unknown diphenylchlorotin carboxylates (Ph2SnX′Cl) indicating cleavage of Ph-Sn bond in preference to Cl-Sn bond. On the basis of the results, it is predicated that these diphenylchlorotin carboxylates possess bridging carboxylate groups (inter-molecularly chelated structure) in the solid state, whereas in solution they contain chelated carboxylate groups (intra-molecularly chelated structures).
New Observations Concerning the Reactivity of Triorganotin Fluorides
Lambertsen, Thomas,Schmutzler, Reinhard
, p. 1583 - 1586 (2007/10/03)
Me3SnF (1) reacts with many hydrolyzable chlorides to give Me3SnCl and the corresponding fluoride.The formation of PhPF2, (ClCH2)MeSiF2, F2PCH2PF2 and PF5 is described.The reaction of triorganotin fluorides (Ph3SnF, Bu3SnF) with CaBr2 yields pure triorganotin bromides. 1 was found to act either as a fluoride-acceptor or, towards PF5, as a fluoride-donor. - Keywords: Trimethylfluorostannane; Triorganohalo-Stannanes; Phosphorus-Fluorine Compounds; NMR Spectra
Interaction of naphthaleneytterbium with tetraphenyltin. Molecular structure of Ph3SnYb(THF)2(μ-Ph)3Yb(THF)3
Bochkarev, Mikhail N.,Khramenkov, Vladimir V.,Rad'kov, Yury F.,Zakharov, Lev N.,Struchkov, Yury T.
, p. 29 - 38 (2007/10/02)
Reaction of naphthaleneytterbium with Ph4Sn in THF yields (Ph3Sn)2Yb(THF)4 and the heteroleptic complex Ph3SnYb(THF)2(μ-Ph)3Yb(THF)3 (1), which can be isolated by crystallization from THF/ether solution.The product 1 forms triclinic crystals in space group P1 with a = 11.123(2), b = 14.078(3), c = 18.774(4) Angstroem, α = 101.94(2), β = 96.20(2), γ = 109.85(2) deg, Z = 2.Least-squares refinement on the basis of 4955 reflections led to a final R value of 0.027.The molecule of 1 contains two Yb atoms connected by three bridging Ph rings.One of Yb atoms is bonded with Ph3Sn unit (Sn-Yb bond length is 3.379(1) Angstroem) and two THF molecules.The second Yb atom is surrounded by three molecules of coordinated THF.Coordination of each ytterbium atom is distorted octahedron.The proposed reaction scheme includes two-electron oxidation of naphthaleneytterbium, formation of Ph3SnYbPh and PhYbPh intermediates and their following association.
HALOGEN AND PEUDOHALOGEN SUBSTITUTION OF SOME ADAMANTANOID CHALCOGENATE CLUSTERS (2-) USING METHYLMERCURY AND TRIPHENYLTIN DERIVATIVES. A MULTINUCLEAR NUCLEAR MAGNETIC RESONANCE STUDY
Dean, Philip A. W.,Vittal, Jagadese J.
, p. 2443 - 2451 (2007/10/02)
Multinuclear nmr (1H, 77Se, 111/113Cd, 119Sn, 199Hg, as appropriate) has been used to study Y(1-) - EPh(1-) exchange in Me2CO or MeCN between (RnM'Y (RnM' = Ph3Sn or MeHg; Y = Cl, Br, I, NCO, or NCS) and the adamantane-like anions (2-) (E = S, M = Zn, Cd, or Co; E = Se, M = Zn or Cd), as their tetraalkylammonium salts.Quantitative terminal substitution of the clusters occurs in most cases, giving 4-x(MY)x>(2-) (x = 1-4).However, reaction is incomplete for M = Cd, E = S or Se, RnM'Y = Ph3SnNCO or Ph3SnNCS and for M = Zn or Co, E = S, RnM'Y = MeHgI.Differences in the extents of reaction for Ph3SnY and MeHgY are consistent with the position of equilibrium in MeHgY:Ph3SnEPh mixtures.Group interchange provides a convenient alternative synthesis of the known halogen-substituted clusters (2-) (M = Zn or Cd, Y = Cl, Br, or I; M = Co, Y = Cl), and the first syntheses of (2-) (Y = Br or I) and various pseudohalogen-substituted adamantanoid anions.The nuclei used for full direct nmr characterization of the new clusters in solution were: 77Se and 113Cd for 4-x(CdY)x>(2-) (x = 1-4; Y = NCO or NCS); 77Se for 4-x(ZnY)x>(2-) (x = 1-4, Y = NCO or NCS); 113Cd for 4-x(CdY)x>(2-) (x = 1-4; Y = NCO or NCS); 1H for (2-) (Y = Br, I, NCO, or NCS).The first solution 1H nmr spectrum of (2-) is also reported.
THE INSERTION OF INDIUM(I) HALIDES INTO THE M-X BOND OF SOME MAIN GROUP ORGANOMETALLIC HALIDES
Annan, Theodore A.,Tuck, Dennis G.
, p. 83 - 90 (2007/10/02)
Indium(I) halides (InX) react with Ph3SnX (X=Cl, Br, I) in toluene/tmed mixtures to give Ph3SnInX2*tmed compounds (tmed=N,N,N',N'-tetramethylethanediamine), and Ph3Sn(OAc) yields Ph3SnIn(OAc)X2*tmed.Vibrational spectra and conductivities of these compounds, and of the salt Et4N, show that these are the first examples of Sn-In bonded molecules.With Me3SnCl, Ph3SnH, Ph3GeCl, Ph3PbCl and Ph2PCl, no oxidative addition reaction was observed.The results are compatible with previous discussions of the mechanism of such reactions, based on the insertion of indium into the M-X bond.
PREPARATION AND SPECTROSCOPIC STUDIES OF SOME CYCLIC UREA ADDUCTS OF TRIPHENYL-THIN AND -LEAD HALIDES
Aitken, Clare T.,Onyszchuk, Mario
, p. 149 - 158 (2007/10/02)
1,3-Dimethyl-2-imidazolidinone (dimethylethylene urea, DMEU) and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (dimethylpropylene urea, DMPU) adducts of the type Ph3SnX*L (X = Cl, Br and I), Ph3PbX*L (X = Br, I), 3Ph3PbCl*2DMEU and 2Ph3PbCl*DMPU have been prepared and characterized.Assignments are made for ν(CO) and ν(CN) frequencies in the IR, and for skeletal frequencies observed in both IR and Raman spectra in the range 400 to 100 cm-1.Infrared measurements show that the adducts are bound through the carbonyl oxygen, and are highly dissociated in dichloromethane solution. 1H and 119 Sn or 207Pb NMR measurements reveal that ligand exchange, fast on the NMR time scale, occurs in solution.Coordination of the ligand causes a large upfield shift in the 119Sn or 207Pb resonances, but Ph3MI*L have shifts similar to those for the parent iodides, indicating almost complete dissociation.Thermodynamic parameters are reported for the dissociation of Ph3SnX*DMPU (X = Cl, Br) in Ch2Cl2 solution
SYNTHESIS OF TRIPHENYLPHOSPHONOPROPIONBETAINETRIORGANOTIN(IV) SALTS +X-, BY NUCLEOPHILIC DISPLACEMENT OF ANIONS FROM TRIORGANOTINS
Ng, S. -W.,Zuckerman, J. J.
, p. 257 - 276 (2007/10/02)
Trimethyl- and triphenyl-tin(IV) hydroxide act on triphenyl(2-carboxyethyl)-phosphonium hydrochloride, which is made from 3-chloropropionic acid and triphenylphosphine, to release water in the presence of dimethylformamide (DMF) as a catalyst.The water is azeotropically distilled to drive the reaction forward and produce triphenylphosphonopropionbetainetrimethyl- and triphenyl-tin(IV) chlorides in high yield.The latter product also results from the displacement of chloride from triphenyltin(IV) chloride by the phosphobetaine, (C6H5)3P(CH2)2CO2, which is made by treating the phospnonium hydrochloride with bicarbonate, and the compounds + X- where X = Cl, Br, I, N3, NCS, NO3, B(C6H5)4 and Co(CO)4 are made in the same way.The acetate salt results from metathesis from the chloride and lead(II) acetate.A double salt, + -, is formed for X = Cl, Br, and N3 by adding additional (C6H5)3SnX to the already-formed simple salts.Double salts are also obtained from the 1/1 reactions between the phosphobetaine and triphenyltin(IV) isocyanate and methyldiphenyltin(IV) chloride.The phosphonium chloride double salt could be converted to the thiophosphonium derivative by heating with elemental sulfur in ethanol.The products of these novel nucleophilic displacement reactions are high melting solids.Tin-119m Moessbauer data are consistent with five-coordinated, triorganotin(IV) formulations with the exception of the diphenyl(8-hydroxyquinolinato)tin(IV) chloride salt in which the tin atom is six-coordinated, and the diphenyltin system cis-oriented.The parameters otherwise do not change with the nature of the X group, which in the tetracarbonylcobaltate derivative is tetrahedral by infrared, establishing the ionicity of the products.The chloride exhibits a molar conductivity indicative of a 1/1 electrolyte in DMF.A bridging acetate structure in the solid is consistent with the lowered v(CO2) frequencies.The Moessbauer spectra of the double salts give simple doublets of lowered isomer shift (IS) and raised quadrupole splitting (QS) which may arise from a cross-linking ion pairing of the...
Reactions of Tin-Naphthyl Bond with Halogens and Pseudohalogens
Bhattacharya, S. N.,Husain, Ishrat
, p. 1119 - 1121 (2007/10/02)
Reactivity of Sn-phenyl or Sn-naphthyl bond in tetraorganotins, PhnSnNp4-n (Ph = phenyl, Np = α-naphthyl; n = 2,3) towards halogens (Br2 and I2), interhalogens (IBr and ICl), interpseudohalogens (BrCN and ICN) and pseudohalogen (SCN)2 has been studied.It is found that the Sn-Np bond is preferentially cleaved yielding in most cases phenyltin derivatives along with the corresponding α-naphthyl halides.
