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The polymerization of styrene with novel catalytic systems of anilido-imino nickel complexes (Ar1N = CHC6H4NAr2) NiBr (Ar1 = Ar2 = 2,6-dimethylphenyl, 1; Ar1 = 2,6-dimethylphenyl, Ar2 = 2,6-diisopropylphenyl, 2; Ar1 = Ar2 = 2,6-diisopropylphenyl, 3; Ar1 = 2,6-diisopropylphenyl, Ar2 = 2,6-dimethylphenyl, 4) activated by methylaluminoxane was investigated. The influence of reaction parameters (temperature, Al/Ni mole ratio, and polymerization time) on styrene polymerization was evaluated. The influence of the bulkiness of the substituents on polymerization activity and polymer characteristics was also ascertained. The obtained polystyrene was an iso-rich atactic polymer and its weight-average molecular weight reached 70 500. NMR analysis of the end groups further confirmed that styrene polymerization catalyzed by anilido-imino nickel complexes/MAO systems proceeded through a coordination mechanism, and the chain was initiated through styrene secondary insertion into the NiH and terminated mainly through β-H elimination of styrene producing the chain-end group (CHCHPh). 相似文献
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Esther Delgado Elisa Hernández Avelino Martín 《Journal of organometallic chemistry》2010,695(3):446-11252
The multifunctional ligands [(Z)-FcCCSC(H)C(H)XR] [X = O, R = Me (2a); X = O, R = Et (2b); X = S, R = Ph (3); X = S, R = C6F5 (5)] and [(Z,Z)-Fc(SR)CC(H)SC(H)C(H)SR] [R = Ph (4), C6F5 (6)] have been prepared through hydroalkoxylation and hydrothiolation processes of the alkyne groups in the compound FcCCSCCH 1. Reactions between compound 3 and the carbonyl metals Co2(CO)8, Os3(CO)10(NCMe)2 and Fe2(CO)9 have allowed the synthesis of the polynuclear compounds [(Z)-{Co2(CO)6}(μ-η2-FcCCSC(H)C(H)SPh)] 9, [(Z)-Os3(CO)9(μ-CO){μ3-η2-FcCCSC(H)C(H)(SPh)}] 10 and [(Z)-{Fe3(CO)9}[μ3,η3-(CCS)-FcCCSC(H)C(H)(SPh)] 11. All the compounds have been characterized by elemental analysis, 1H and 13C{1H} NMR spectroscopy, mass spectrometry and the crystal structure of compounds [(Z)-FcCCSC(H)C(H)OMe] 2a and [{Co2(CO)6}2(μ-η2:η2-FcCCSCCSiMe3)] 7 have been solved by X ray diffraction analysis. 相似文献
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Javier Martínez José M. Antelo Juan M. Ortigueira Jesús J. Fernández José M. Vila 《Journal of organometallic chemistry》2006,691(12):2721-2733
Treatment of the thiosemicarbazones 2-XC6H4C(Me)NN(H)C(S)NHR (R = Me, X = F, a; R = Et, X = F, b; R = Me, X = Cl, c; R = Et, X = Br, d) with potassium tetrachloropalladate(II) in ethanol, lithium tetrachloropalladate(II) in methanol or palladium(II) acetate in acetic acid, as appropriate, gave the tetranuclear cyclometallated complexes [Pd{2-XC6H3C(Me)NNC(S)NHR}]4 (1a-1d). Reaction of 1a-1d with the diphosphines Ph2PCH2PPh2 (dppm), Ph2P(CH2)2PPh2 (dppe), Ph2P(CH2)3PPh2 (dppp) or trans-Ph2PCHCHPPh2 (trans-dpe) in 1:2 molar ratio gave the dinuclear cyclometallated complexes [{Pd[2-XC6H3C(Me)NNC(S)-NHR]}2(μ-diphosphine-P,P)] (2a-5a, 3b, 3d, 4c, 5c). Reaction of 1a, 1b with the short-bite or long-bite diphosphines, dppm or cis-dpe, in a 1:4 molar ratio gave the mononuclear cyclometallated complexes [Pd{2-XC6H3C(Me)NNC(S)NHR}(diphosphine-P)] (6a, 6b, 7a). The molecular structure of ligand a and of complexes 1a, 3d, 5a, 5c, 6a, 6b and 7a have been determined by X-ray diffraction analysis. The structure of complex 7a shows that the long-bite cis-bis(diphenylphosphino)ethene phosphine appears as monodentate with an uncoordinated phosphorus donor atom. 相似文献
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Nicholas A. Barnes Cheryl Fish James V. Morey Robin G. Pritchard John E. Warren 《Journal of fluorine chemistry》2010,131(11):1156-1164
The coordination chemistry of the fluorovinyl substituted phosphines PPh2(Z-CFCFH) and PPh2(E-CClCFH) with K2MX4 (M = Pd, Pt; X = Cl, Br, and I) salts has been investigated resulting in the first reported palladium(II) and platinum(II) complexes of phosphines containing partially fluorinated vinyl groups. The complexes have been characterised by a combination of multinuclear [1H, 13C{1H}, 19F, 31P{1H}] NMR spectroscopy, and IR/Raman spectroscopy. The single-crystal X-ray structures of trans-[PdX2{PPh2(CFCFH)}2], X = Cl (1), Br (2), I (3), trans-[PdCl2{PPh2(CClCFH)}2] (4), cis-[PtX2{PPh2(CFCFH)}2], X = Cl (5), Br (6), trans-[PtI2{PPh2(CFCFH)}2] (7), and both cis- and trans-[PtCl2{PPh2(CClCFH)}2] (8), have been determined. Results obtained from spectroscopic and crystallographic data suggest that replacement of a β-fluorine by hydrogen, whilst reducing the steric demand of the ligand, has little effect on the electronic character of the ligand. The presence of a proton in the vinyl group results in short proton-halide secondary interactions in the solid state (d(H?X) = 2.72(3) for 1, and 2.92(5) Å for 2) forming an infinite chain ribbon motif. 相似文献
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Rainer Schobert Rhett Kempe Alexander Gmeiner 《Journal of organometallic chemistry》2006,691(5):859-868
The metallacyclic complexes (OC)4MC(η2-NHCH2CHCHX)Fc (4; X = H) and (5; X = CH2OH) [M = Cr: a; Mo: b; W: c; Fc = ferrocenyl = CpFe(C5H4)] were obtained in good yields upon photo-decarbonylation of the bimetallic allylaminocarbene complexes (OC)5MC(NHCH2CHCHX)Fc (2; X = H)/(3; X = CH2OH). At room temperature complexes 2/3 exist as mixtures of E- and predominantly Z-isomers with regard to the C-N bond. The molecular structures of 4b and 4c were determined by X-ray diffraction analyses. The intermetallic communicative effects and the interplay of Fc and η2-alkene moieties of 4a and 4b were assessed by cyclovoltammetry. All complexes were also characterized in solution by one- and two-dimensional NMR spectroscopy (1H, 13C, 1H NOE, 1H/1H COSY, 13C/1H HETCOR). 相似文献
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Luigi Busetto Fabio Marchetti Rita Mazzoni Stefano Zacchini 《Journal of organometallic chemistry》2008,693(13):2383-2391
The zwitterionic vinyliminium complex [Fe2{μ-η1:η3-C(R′)C(S)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (2a) (R′ = p-Me-C6H4 (Tol), Xyl = 2,6-Me2C6H3) undergoes electrophilic addition at the S atom by HSO3CF3, MeSO3CF3, SiMe3Cl, BrCH2Ph, ICH2CHCH2 affording the complexes [Fe2{μ-η1:η3-C(Tol)C(SX)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][Y] (X = H, Y = SO3CF3, 4a; X = Me, Y = SO3CF3, 4b; X = SiMe3, Y = Cl, 4c; X = CH2Ph, Y = Br, 4d; X = CH2CHCH2, Y = I, 4e).Compound 2a and the corresponding vinyliminium complexes 2b and 2c (R′ = CH2OH, 2b; R′ = Me, 2c) react also with etherated BF3 leading to the formation of the corresponding S-adducts [Fe2{μ-η1:η3-C(R′)C(SBF3)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (R′ = Tol, 5a; R′ = CH2OH, 5b; R′ = Me, 5c).In analogous reactions, the zwitterionic vinyliminium complexes undergo S-metalation upon treatment with in situ generated [Fp]+[SO3CF3]− [Fp = Fe(CO)2(Cp)], leading to the formation of [Fe2{μ-η1:η3-C(R′)C(S-Fp)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3](R′ = CH2OH, 6a; R′ = Me, 6b; R′ = Bun, 6c).Similarly, zwitterionic vinyliminium containing Se in the place of S also undergo Se-electrophilic addition. Thus, the complexes [Fe2{μ-η1:η3-C(R′)C(SeX)CN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = X = Me, R′ = Tol, 7a; R = Xyl, R′ = Me, X = Fp+, 7b) are obtained upon treatment of the neutral zwitterionic precursors with MeSO3CF3 and [Fp][SO3CF3], respectively.Alkylation at the S or Se atom of the bridging ligand is also accomplished by CH2Cl2, used as solvent, although the reaction is slower compared to more efficient alkylating reagents. The complexes formed by this route are [Fe2{μ-η1:η3-C(R′)C(E-CH2Cl)CN(Me)(R)}(μ-CO)(CO)(Cp)2][X] [E = S, R = Xyl, R′ = Tol, X = Cl, 8a; E = S, R = Xyl, R′ = Me, X = Cl, 8b; E = Se, R = R′ = Me, X = BPh4, 8c].Finally, treatment of the zwitterionic vinyliminium complexes with I2 results in the oxidative coupling with formation of S-S (disulfide) or Se-Se (diselenide) bond. The reactions, performed in the presence of NaBPh4 afford the tetranuclear complexes [Fe2{μ-η1:η3-C(R′)C(E)CN(Me)(R)}(μ-CO)(CO)(Cp)2]2[BPh4]2 [R = Xyl, R′ = CH2OH, E = S, 9a; R = Xyl, R′ = Me, E = S, 9b; R = Xyl, R′ = Bun, E = S, 9c; R = Xyl, R′ = Me, E = Se, 9d; R = Me, R′ = Bun, E = Se, 9e].The molecular structures of 4a, 8c and 9e have been determined by X-ray diffraction studies. 相似文献
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Luigi Busetto Rita Mazzoni Stefano Zacchini 《Journal of organometallic chemistry》2008,693(19):3191-3196
The SPh functionalized vinyliminium complexes [Fe2{μ-η1:η3-Cγ(R′)Cβ(SPh)CαN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] [R = Xyl, R′ = Me, 2a; R = Me, R′ = Me, 2b; R = 4-C6H4OMe, R′ = Me, 2c; R = Xyl, R′ = CH2OH, 2d; R = Me, R′ = CH2OH, 2e; Xyl = 2,6-Me2C6H3] are generated in high yields by treatment of the corresponding vinyliminium complexes [Fe2{μ-η1:η3-Cγ(R′)Cβ(H)CαN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (1a-e) with NaH in the presence of PhSSPh. Likewise, the diruthenium complex [Ru2{μ-η1:η3-Cγ(Me)Cβ(SPh)CαN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (2f) was obtained from the corresponding vinyliminium complex [Ru2{μ-η1:η3-Cγ(Me)Cβ(H)CαN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (1f). The synthesis of 2c is accompanied by the formation, in comparable amounts, of the aminocarbyne complex [Fe2{μ-CN(Me)(4-C6H4OMe)}(SPh)(μ-CO)(CO)(Cp)2] (3).The molecular structures of 2d, 2e and 3 have been determined by X-ray diffraction studies. 相似文献
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Victorio Cadierno 《Journal of organometallic chemistry》2005,690(8):2087-2096
The novel bis(iminophosphorano)methanes CH2[P{NP(S)(OR)2}Ph2]2 (R = Ph (1a), Et (1b)) have been obtained by oxydation of dppm with the corresponding thiophosphorylated azides (RO)2P(S)N3. Deprotonation of 1a,b with KH generates the methanide species KCH[P{NP(S)(OR)2}Ph2]2 (R = Ph (2a), Et (2b)). The ruthenium(II) dimer [{Ru(η6-p-cymene)(μ-Cl)Cl}2] reacts with 2a,b to afford the cationic complexes [Ru(η6-p-cymene)(κ3-C,N,S-CH[P{NP(S)(OR)2}Ph2]2)]+ (R = Ph (3a), Et (3b)), via selective κ3-C,N,S-coordination of the bis(iminophosphorano)methanide anions to ruthenium. The structure of [Ru(η6-p-cymene)(κ3-C,N,S-CH[P{NP(S)(OEt)2}Ph2]2)][PF6] (3b) has been confirmed by single-crystal X-ray crystallography. Deprotonation of complexes 3a,b with NaH leads to the neutral carbene derivatives [Ru(η6-p-cymene)(κ2-C,N-C[P{NP(S)(OR)2}Ph2]2)] (R = Ph (4a), Et (4b)). 相似文献
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Javier Martínez José M. Antelo Ma Teresa Pereira José M. Vila 《Journal of organometallic chemistry》2006,691(13):2891-2901
Treatment of the thiosemicarbazones 4-FC6H4C(Me)NN(H)C(S)NHR, (R = Me, a; Ph, b) and 2-ClC6H4C(Me)NN(H)C(S)NHR (R = Ph, c) with lithium tetrachloropalladate(II) in methanol or palladium(II) acetate in acetic acid gave the tetranuclear cyclometallated complex [Pd{4-FC6H3C(Me)NNC(S)NHR}]4 (1a, 1b) and [Pd{2-ClC6H3C(Me)NNC(S)NHPh}]4 (1c). Reaction of these tetramers with the diphosphines dppe, t-dppe, dppp or dppb in a 1:2 molar ratio gave the dinuclear cyclometallated complexes [(Pd{4-FC6H3C(Me)NNC(S)NHR})2(μ-Ph2P(CH2)nPPh2)], (n = 2, 2a, 2b; 3, 4a, 4b; 4, 5a, 5b), [(Pd{4-FC6H3C(Me)NNC(S)NHPh})2(μ-Ph2PCHCHPPh2)], (3a, 3b) and [(Pd{2-ClC6H3C(Me)NNC(S)NHR})2(μ-Ph2P(CH2)nPPh2)], (n = 2, 2c, 2d; 3, 4c, 4d; 4, 5c, 5d), [(Pd{2-ClC6H3C(Me)NNC(S)NHPh})2(μ-PPh2CHCHPPh2)], (3c, 3d). The X-ray crystal structure of the ligand b and the complexes 3c, 4a and 4d were determined. The structures of complexes 4a and 4d show that the different disposition of the chain cyclometallated of the thiosemicarbazones (in the same orientation or in the opposite one) is due to the different H bonds produced. 相似文献