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1.
Rosa M. Ceder Arnald Grabulosa Guillermo Muller Mercè Font-Bardía 《Journal of organometallic chemistry》2007,692(19):4005-4019
Optically active ligands of type Ph2PNHR (R = (R)-CHCH3Ph, (a); (R)-CHCH3Cy, (b); (R)-CHCH3Naph, (c)) and PhP(NHR)2 (R = (R)-CHCH3Ph, (d); (R)-CHCH3Cy, (e)) with a stereogenic carbon atom in the R substituent were synthesized. Reaction with [PdCl2(COD)2] produced [PdCl2P2] (1) (P = PhP(NHCHCH3Ph)2), whose molecular structure determined by X-ray diffraction showed cis disposition for the ligands. All nitrogen atoms of amino groups adopted S configuration. The new ligands reacted with allylic dimeric palladium compound [Pd(η3-2-methylallyl)Cl]2 to gave neutral aminophosphine complexes [Pd(η3-2-methylallyl)ClP] (2a-2e) or cationic aminophosphine complexes [Pd(η3-2-methylallyl)P2]BF4 (3a-3e) in the presence of the stoichiometric amount of AgBF4. Cationic complexes [Pd(η43-2-methylallyl)(NCCH3)P]BF4 (4a-4e) were prepared in solution to be used as precursors in the catalytic hydrovinylation of styrene. 31P NMR spectroscopy showed the existence of an equilibrium between the expected cationic mixed complexes 4, the symmetrical cationic complexes [Pd(η3-2-methylallyl)P2]BF4 (3) and [Pd(η3-2-methylallyl)(NCCH3)2]BF4 (5) coming from the symmetrization reaction. The extension of the process was studied with the aminophosphines (a-e) as well as with nonchiral monodentate phosphines (PCy3 (f), PBn3 (g), PPh3 (h), PMe2Ph (i)) showing a good match between the extension of the symmetrization and the size of the phosphine ligand. We studied the influence of such equilibria in the hydrovinylation of styrene because the behaviour of catalytic precursors can be modified substantially when prepared ‘in situ’. While compounds 3 and bisacetonitrile complex 5 were not active as catalysts, the [Pd(η3-2-methylallyl)(η2-styrene)2]+ species formed in the absence of acetonitrile showed some activity in the formation of codimers and dimers. Hydrovinylation reaction between styrene and ethylene was tested using catalytic precursors solutions of [Pd(η3-2-methylallyl)LP]BF4 ionic species (L = CH3CN or styrene) showing moderate activity and good selectivity. Better activities but lower selectivities were found when L = styrene. Only in the case of the precursor containing Ph2PNHCHCH3Ph (a) ligand was some enantiodiscrimination (10%) found. 相似文献
2.
Anshu Singhal Dimple P. Dutta Shaikh M. Mobin Ingo Lieberwirth 《Journal of organometallic chemistry》2007,692(23):5285-5294
In an effort to find simple and common single-source precursors for palladium sulfide nanostructures, palladium(II) complexes, [Pd(S2X)2] (X = COMe (1), COiPr (2)) and η3-allylpalladium complexes with xanthate ligands, [(η3-CH2C(CH3)CR2)Pd(S2X)] (R = H, X = COMe (3); R = H, X = COEt (4); R = H, X = COiPr (5); R = CH3, X = COMe (6)), have been investigated. The crystal structures of [Pd(S2X)2] (X = COMe (1), CoiPr (2)) and [(η3-CH2C(CH3)CH2)Pd(S2COMe)] (3) have been established by single crystal X-ray diffraction analysis. The complexes, 1, 2 and 3 all contain a square planar palladium(II) centre. In the allyl complex 3, this is defined by the two sulfurs of the xanthate and the outer carbons of the 2-methylallyl ligand, while in the complexes, 1 and 2 it is defined by the four sulfur atoms of the xanthate ligand. Thermogravimetric studies have been carried out to evaluate the thermal stability of η3-allylpalladium(II) analogues. The complexes are useful precursors for the growth of nanocrystals of PdS either by furnace decomposition or solvothermolysis in dioctyl ether. The solvothermal decomposition of complexes in dioctyl ether gives a new metastable phase of PdS which can be transformed to the more stable tetragonal phase at 320 °C. The nanocrystals obtained have been characterized by PXRD, SEM, TEM and EDX. 相似文献
3.
Swadhin K. Mandal 《Journal of organometallic chemistry》2006,691(13):2969-2977
The chemistry of η3-allyl palladium complexes of the diphosphazane ligands, X2PN(Me)PX2 [X = OC6H5 (1) or OC6H3Me2-2,6 (2)] has been investigated.The reactions of the phenoxy derivative, (PhO)2PN(Me)P(OPh)2 with [Pd(η3-1,3-R′,R″-C3H3)(μ-Cl)]2 (R′ = R″ = H or Me; R′ = H, R″ = Me) give exclusively the palladium dimer, [Pd2{μ-(PhO)2PN(Me)P(OPh)2}2Cl2] (3); however, the analogous reaction with [Pd(η3-1,3-R′,R″-C3H3)(μ-Cl)]2 (R′ = R″ = Ph) gives the palladium dimer and the allyl palladium complex [Pd(η3-1,3-R′,R″-C3H3)(1)](PF6) (R′ = R″ = Ph) (4). On the other hand, the 2,6-dimethylphenoxy substituted derivative 2 reacts with (allyl) palladium chloro dimers to give stable allyl palladium complexes, [Pd(η3-1,3-R′,R″-C3H3)(2)](PF6) [R′ = R″ = H (5), Me (7) or Ph (8); R′ = H, R″ = Me (6)].Detailed NMR studies reveal that the complexes 6 and 7 exist as a mixture of isomers in solution; the relatively less favourable isomer, anti-[Pd(η3-1-Me-C3H4)(2)](PF6) (6b) and syn/anti-[Pd(η3-1,3-Me2-C3H3)(2)](PF6) (7b) are present to the extent of 25% and 40%, respectively. This result can be explained on the basis of the steric congestion around the donor phosphorus atoms in 2. The structures of four complexes (4, 5, 7a and 8) have been determined by X-ray crystallography; only one isomer is observed in the solid state in each case. 相似文献
4.
Shaowu Wang Shaoyin Wang Gaosheng Yang Nan Hu Hai-Bin Song 《Journal of organometallic chemistry》2007,692(10):2099-2106
Two series of new divalent organolanthanide complexes with the general formula [η5:η1-{1-R-3-(C5H9OCH2)C9H5}]2LnII (R = H, Ln = Yb (3); R = Me3Si, Ln = Yb (4); R = H, Ln = Eu (5); R = Me3Si, Ln = Eu (6)) were prepared by reactions of 2 equiv. of 1-R-3-(C5H9OCH2)C9H6 (R = H (1), R = Me3Si (2)) with the lanthanide(III) amides [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 (Ln = Yb, Eu) via a one-electron reductive elimination process. Recrystallization of 6 from n-hexane afforded [η5:η1-(C5H9OCH2C9H5SiMe3)]2EuII · (C6H14)0.5 (7). All compounds were fully characterized by elemental analyses, and spectroscopic methods. The structures of complexes 4 and 7 were additionally determined by single-crystal X-ray analyses. The catalytic activity of the complexes on methyl methacrylate and ε-caprolactone polymerization was studied, and the temperatures, substituents on the indenyl ring, and solvents effects on the catalytic activity of the complexes were examined. 相似文献
5.
《Journal of organometallic chemistry》2011,696(26):4281-4292
Cp-functionalized monotroticenes [(η7-C7H7)Ti(η5-C5H4E)] (2, E = Ph2SiCl; 3, E = tBu2SnCl; 12, E = I) and bitroticenes [(η7-C7H7)Ti(η5-C5H4)]2E′ (5, E′ = PPh; 6, E′ = BN(SiMe3)2; 7, E′ = Cp2Ti) were prepared by salt elimination metathesis between the monolithiated troticene [(η7-C7H7)Ti(η5-C5H4Li)]·pmdta (1b) (pmdta = N,N′,N′,N″,N″-pentamethyldiethylene-triamine) and the appropriate electrophile. The troticenyl-substituted zirconocene monochloride [(η7-C7H7)Ti(η5-C5H4ZrClCp*2)] (Cp* = η5-C5Me5) (8) and hafnocene ethoxide [(η7-C7H7)Ti{η5-C5H4Hf(OEt)Cp2}] (Cp = η5-C5H5) (11), and the heterobimetallic μ-oxo complexes [(η7-C7H7)Ti(η5-C5H4MCp2)]2O (9, M = Zr; 10, M = Hf) were obtained instead of the expected zircona- and hafna[1]troticenophanes by reaction of the dilithiated troticene [(η7-C7H6Li)Ti(η5-C5H4Li)]·pmdta (1a) with [Cp2MCl2] (M = Zr, Hf) or [Cp*2ZrCl2] in stoichiometric amounts. These compounds were characterized by single crystal X-ray diffraction analyses and, in the case of 2, 3, 5–7, 9, 10 and 12, also by elemental analyses and 1H, 13C and 119Sn NMR spectroscopy. Exposure of the troticenyl organotin chloride 3 to moisture resulted in its partial hydrolysis and formation of the organostannoxane-bridged bitroticene 4, while palladium-catalyzed Negishi C–C cross-coupling reaction between the troticenylzinc chloride [(η7-C7H7)Ti(η5-C5H4ZnCl)] (13) and the iodotroticene 12 or iodobenzene (PhI) led to the fulvalene complexes [(η7-C7H7)Ti(η5-C5H4)]2 (14) and [(η7-C7H7)Ti(η5-C5H4Ph)] (15). Compound 4 displays an unsymmetrical structure with the troticenyl fragments cis with respect to the Sn–O–Sn core, whereas compound 14 is centrosymmetrically trans oriented. 相似文献
6.
Alain C. Tagne Kuate Swagat K. Mohapatra Constantin G. Daniliuc Peter G. Jones Matthias Tamm 《Journal of organometallic chemistry》2012,696(26):4281-4292
Cp-functionalized monotroticenes [(η7-C7H7)Ti(η5-C5H4E)] (2, E = Ph2SiCl; 3, E = tBu2SnCl; 12, E = I) and bitroticenes [(η7-C7H7)Ti(η5-C5H4)]2E′ (5, E′ = PPh; 6, E′ = BN(SiMe3)2; 7, E′ = Cp2Ti) were prepared by salt elimination metathesis between the monolithiated troticene [(η7-C7H7)Ti(η5-C5H4Li)]·pmdta (1b) (pmdta = N,N′,N′,N″,N″-pentamethyldiethylene-triamine) and the appropriate electrophile. The troticenyl-substituted zirconocene monochloride [(η7-C7H7)Ti(η5-C5H4ZrClCp*2)] (Cp* = η5-C5Me5) (8) and hafnocene ethoxide [(η7-C7H7)Ti{η5-C5H4Hf(OEt)Cp2}] (Cp = η5-C5H5) (11), and the heterobimetallic μ-oxo complexes [(η7-C7H7)Ti(η5-C5H4MCp2)]2O (9, M = Zr; 10, M = Hf) were obtained instead of the expected zircona- and hafna[1]troticenophanes by reaction of the dilithiated troticene [(η7-C7H6Li)Ti(η5-C5H4Li)]·pmdta (1a) with [Cp2MCl2] (M = Zr, Hf) or [Cp*2ZrCl2] in stoichiometric amounts. These compounds were characterized by single crystal X-ray diffraction analyses and, in the case of 2, 3, 5–7, 9, 10 and 12, also by elemental analyses and 1H, 13C and 119Sn NMR spectroscopy. Exposure of the troticenyl organotin chloride 3 to moisture resulted in its partial hydrolysis and formation of the organostannoxane-bridged bitroticene 4, while palladium-catalyzed Negishi C–C cross-coupling reaction between the troticenylzinc chloride [(η7-C7H7)Ti(η5-C5H4ZnCl)] (13) and the iodotroticene 12 or iodobenzene (PhI) led to the fulvalene complexes [(η7-C7H7)Ti(η5-C5H4)]2 (14) and [(η7-C7H7)Ti(η5-C5H4Ph)] (15). Compound 4 displays an unsymmetrical structure with the troticenyl fragments cis with respect to the Sn–O–Sn core, whereas compound 14 is centrosymmetrically trans oriented. 相似文献
7.
《Journal of organometallic chemistry》2005,690(24-25):5654-5661
Palladium–biscarbene complexes derived from N,N′-bis(1,2,4-triazol-1-yl)methane, which bear an alkyl chain functionalized with a hydroxyl group, have been synthesized ([Pd(L1)Br2] (6) and [Pd(L1)I2] (7) [L1 = 1,1′-(3-hydroxypropylidene)bis(4-butyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene)]). Each product is obtained as a non-equimolecular mixture of two conformers. The hydroxyl group has been replaced by bromide and methanesulphonate and ( [Pd(L2)Br2] [L2 = 1,1′-(3-bromopropylidene)bis(4-butyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene)] (9)) and ([Pd(L3)Br2] [L3 = 1,1′-(3-methanesulphonyloxypropylidene)-bis(4-butyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene)] (10)) were obtained, respectively, as mixtures of conformers. All compounds consist of a six-membered metallacyclic structure in a boat conformation. Major conformers present the functionalized chain in the axial position, while in minor conformers it is located in the equatorial position. 相似文献
8.
Vincenzo G. Albano Fabio Marchetti Stefano Zacchini 《Journal of organometallic chemistry》2005,690(4):837-846
New μ-vinylalkylidene complexes cis-[Fe2{μ-η1:η3-Cγ(R′)Cβ(R″)CαHN(Me)(R)}(μ-CO)(CO)(Cp)2] (R = Me, R′ = R″ = Me, 3a; R = Me, R′ = R″ = Et, 3b; R = Me, R′ = R″ = Ph, 3c; R = CH2Ph, R′ = R″ = Me, 3d; R = CH2Ph, R′ = R″ = COOMe, 3e; R = CH2 Ph, R′ = SiMe3, R″ = Me, 3f) have been obtained b yreacting the corresponding vinyliminium complexes [Fe2{μ-η1:η3-Cγ(R′)Cβ(R″)CαN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (2a-f) with NaBH4. The formation of 3a-f occurs via selective hydride addition at the iminium carbon (Cα) of the precursors 2a-f. By contrast, the vinyliminium cis-[Fe2{μ-η1:η3-Cγ (R′) = Cβ(R″)Cα = N(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (R′ = R″ = COOMe, 4a; R′ = R″ = Me, 4b; R′ = Prn, R″ = Me, 4c; Prn = CH2CH2CH3, Xyl = 2,6-Me2C6H3) undergo H− addition at the adjacent Cβ, affording the bis-alkylidene complexes cis-[Fe2{μ-η1:η2-C(R′)C(H)(R″)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2], (5a-c). The cis and trans isomers of [Fe2{μ-η1:η3-Cγ(Et)Cβ(Et)CαN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (4d) react differently with NaBH4: the former reacts at Cα yielding cis-[Fe2{μ-η1:η3-Cγ(Et)Cβ(Et)CαHN(Me)(Xyl)}(μ-CO)(CO)(Cp)2], 6a, whereas the hydride attack occurs at Cβ of the latter, leading to the formation of the bis alkylidene trans-[Fe2{μ-η1:η2-C(Et)C(H)(Et)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (5d). The structure of 5d has been determined by an X-ray diffraction study. Other μ-vinylalkylidene complexes cis-[Fe2{μ-η1:η3-Cγ(R′)Cβ(R″)CαHN(Me)(Xyl)}(μ-CO)(CO)(Cp)2], (R′ = R″ = Ph, 6b; R′ = R″ = Me, 6c) have been prepared, and the structure of 6c has been determined by X-ray diffraction. Compound 6b results from treatment of cis-[Fe2{μ-η1:η3-Cγ(Ph)Cβ(Ph)CαN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (4e) with NaBH4, whereas 6c has been obtained by reacting 4b with LiHBEt3. Both cis-4d and trans-4d react with LiHBEt3 affording cis-6a. 相似文献
9.
Vincenzo G. Albano Fabio Marchetti Stefano Zacchini 《Journal of organometallic chemistry》2006,691(20):4234-4243
The diiron vinyliminium complexes [Fe2{μ-η1:η3-C(R′)C(H)CN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R=Me, R′ = SiMe3 (1a); R = Me, R′ = CH2OH (1b); R = CH2Ph, R′ = Tol (1c), Tol = 4-MeC6H4; R = CH2Ph, R′ = COOMe (1d); R = CH2Ph, R′ = SiMe3 (1e)) undergo regio- and stereo-selective addition by cyanide ion (from ), affording the corresponding bridging cyano-functionalized allylidene compounds [Fe2{μ-η1:η3-C(R′)C(H)C(CN)N(Me)(R)}(μ-CO)(CO)(Cp)2] (3a-e), in good yields. Similarly, the diiron vinyliminium complexes [Fe2{μ-η1:η3-C(R′)C(R′)CN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = R′ = Me (2a); R = Me, R′ = Ph (2b); R = CH2Ph, R′ = Me (2c); R = CH2Ph, R′ = COOMe (2d)) react with cyanide and yield [Fe2{μ-η1:η3-C(R′)C(R′)C(CN)N(Me)(R)}(μ-CO)(CO)(Cp)2] (9a-d). The reactions of the vinyliminium complex [Fe2{μ-η1:η3-C(Tol)CHCN(Me)(4-C6H4CF3)}(μ-CO)(CO)(Cp)2][SO3CF3] (4) with NaBH4 and afford the allylidene [Fe2{μ-C(Tol)C(H)C(H)N(Me)(C6H4CF3)}(μ-CO)(CO)(Cp)2] (5) and the cyanoallylidene [Fe2{μ-C(Tol)C(H)C(CN)N(Me)(C6H4CF3)}(μ-CO)(CO)(Cp)2] (6), respectively. Analogously, the diruthenium vinyliminium complex [Ru2{μ-η1:η3-C(SiMe3)CHCN(Me)(CH2Ph)}(μ-CO)(CO)(Cp)2][SO3CF3] (7) reacts with to give [Ru2{μ-η1:η3-C(SiMe3)CHC(CN)N(Me)(CH2Ph)}(μ-CO)(CO)(Cp)2] (8).Finally, cyanide addition to [Fe2{μ-η1:η3-C(COOMe)C(COOMe)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (2e) (Xyl = 2,6-Me2C6H3), yields the cyano-functionalized bis-alkylidene complex [Fe2{μ-η1:η2-C(COOMe)C(COOMe)(CN)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (10). The molecular structures of 3a and 9a have been elucidated by X-ray diffraction. 相似文献
10.
《Journal of organometallic chemistry》2002,641(1-2):62-66
The intense purple colored bi- and trimetallic complexes {Ti}(CH2SiMe3)[CC(η6-C6H5)Cr(CO)3] (3) ({Ti}=(η5-C5H5)2Ti) and [Ti][CC(η6-C6H5)Cr(CO)3]2 (5) {[Ti]=(η5-C5H4SiMe3)2Ti}, in which next to a Ti(IV) center a Cr(0) atom is present, are accessible by the reaction of Li[CC(η6-C6H5)Cr(CO)3] (2) with {Ti}(CH2SiMe3)Cl (1) or [Ti]Cl2 (4) in a 1:1 or 2:1 molar ratio. The chemical and electrochemical properties of 3, 5, {Ti}(CH2SiMe3)(CCFc) [Fc=(η5-C5H5)Fe(η5-C5H4)] and [Ti][(CC)nMc][(CC)mM′c] [n, m=1, 2; n=m; n≠m; Mc=(η5-C5H5)Fe(η5-C5H4); M′c=(η5-C5H5)Ru(η5-C5H4); Mc=M′c; Mc≠M′c] will be comparatively discussed. 相似文献
11.
Eun Seok Park Ji Hae Park Hoseop Yun Bun Yeoul Lee 《Journal of organometallic chemistry》2011,696(11-12):2451-2456
Methylthiophene-fused or dimethylthiophene-fused trimethylcyclopentadienyltitanium trichloride complexes, (η5-Me4RC7S)TiCl3 (R = Me or H), are prepared, from which a chloride ligand is replaced with 2,6-diisopropylphenoxy, di(tert-butyl)ketimide, or tri(tert-butyl)phosphinimide ligand to yield (η5-Me4RC7S)TiXCl2 (11, R = Me, X = iPr2C6H3O–; 12, R = H, X = iPr2C6H3O–; 13, R = Me, X = tBu2C = N–; 14, R = H, X = tBu2C = N–; 15, R = Me, X = tBu3P = N–; 16, R = H, X = tBu3P = N–). The molecular structures of 11, 14, and 16 are confirmed by X-ray crystallography. The Cp(centroid)–Ti–N angles of 11, 14, and 16 (119.83°, 111.98°, and 125.34°, respectively) are significantly larger than the corresponding angle observed for the related thiophene-fused and tetrahydroquinaldine-linked cyclopentadienyl complex (1), [(η5-(Me4C7S)-(2-MeC9H9N-κN)]TiMe2 (106.6°). The phenoxy complexes 11 and 12 show negligible activity, while the ketimido and phosphinimido complexes 13–16 exhibit good activities (5–20 × 106 g/molTi h) for ethylene/1-octene copolymerization. The ketimido-complexes 13 and 14 are able to incorporate a high amount of 1-octene (15–16 mol%), while the phosphinimido-complexes 15 and 16 are not as capable (8 mol% 1-octene) under the identical polymerization conditions. The catalytic performance of 13–16 is inferior to 1 in terms of activity and comonomer incorporation. 相似文献
12.
Piotr Smoleński 《Journal of organometallic chemistry》2011,696(24):3867-3872
Reactions of [(η5-R)Rh(CO)2] (R = cp, ind) with water-soluble phosphines (L = 1,3,5-triaza-7-phosphaadamantane and tris(2-cyanoethyl)phosphine) give the new rhodium(I) complexes of the types [Rh(η5-cp)(CO)(PTA)] (1), [Rh(η5-cp)(CO)(P(CH2CH2CN)3)] (2), [Rh(η5-ind)(CO)(PTA)] (3) and [Rh(η5-ind)(CO)(P(CH2CH2CN)3)] (4) in isolated yields of 52-75%. All these compounds have been fully characterized by IR, 1H, 31P{1H} and 13C{1H} NMR, FAB-MS spectroscopies and elemental analyses. Reactivity for the substitution of phosphine is greater for [(η5-ind)Rh(CO)(L)] comparing to [(η5-cp)Rh(CO)(L)] because of a flexibility of the indenyl ligand to undergo facile η5-η3 coordinative isomerizations. The obtained complexes are active catalyst precursors for the dehydrogenation of propan-2-ol, octane and cyclooctane under photoassisted conditions without any organic hydrogen transfer acceptors, giving TOFs of 26-56 using 3 as precatalyst. 相似文献
13.
《Journal of organometallic chemistry》2004,689(3):552-556
The compounds [Ru3(CO)9(μ,η2-SCCR)(μ3,η2-CCR′)] (R=SiMe3, R′=SiiPr3 (1); R=SiiPr3, R′=SiMe3 (2); R=SiiPr3, R′=H (3); R=H, R′=SiiPr3 (4)) have been obtained by cleavage of one S-C bond of the thioethers iPr3SiCCSCCR (R=H, SiMe3) in the presence of Ru3(CO)12. Thermal treatment of [Ru3(CO)9(μ,η2-SCCSiiPr3)(μ3,η2-CCH)] yields to the cluster [Ru4(CO)9(μ-CO)2(μ4-S)(μ4-η2-C(H)C)(CCSiiPr3)] (5) which contains a bridging sulfur atom and a polycarbon chain as a consequence of the rupture of the S-C bond and a C-C coupling reaction. All derivatives have been characterized by spectroscopic data. An X-ray diffraction study was carried out on the species [Ru3(CO)9(μ,η2-SCCSiiPr3)(μ3,η2-CCSiMe3)] and of [Ru3(CO)9(μ,η2-SCCSiiPr3)(μ3,η2-CCH)]. 相似文献
14.
Manuel Gómez Pilar Gómez-Sal José Manuel Hernández 《Journal of organometallic chemistry》2007,692(11):2291-2298
Trichloro methyl [Nb{η5-C5H3(SiXMe2)(SiMe3)}Cl3Me] (X = Cl, 2; Me, 3), dichloro dimethyl [Nb{η5-C5H3(SiXMe2)(SiMe3)}Cl2Me2] (X = Cl, 4; Me, 5) and tetramethyl [Nb{η5-C5H3(SiXMe2)(SiMe3)}Me4] (X = Me, 6; Cl, 7) niobium complexes were synthesized by treatment of starting tetrachloro derivatives [Nb{η5-C5H3(SiXMe2)(SiMe3)}Cl4] (X = Cl, 1a; Me, 1b) with dimethyl zinc or chloro methyl magnesium in different proportions and conditions. A mixture of trichloro methyl and dichloro dimethyl tantalum complexes [Ta{η5-C5H3(SiClMe2)(SiMe3)}Cl4−xMex] (x = 1, 8; 2, 9) in a 2:1 molar ratio was obtained in the reaction of [Ta{η5-C5H3(SiClMe2)(SiMe3)}Cl4] (1c) with 0.5 equivalents of ZnMe2 in toluene at low temperature. 8 could be isolated as single compound when 1 equivalent of 1c was added to the mixtures of 8 and 9, while the reaction of 1c with 1.5 equivalents of dimethyl zinc gave 9 as unitary product. However, [Ta{η5-C5H3(SiMe3)2}Cl4] (1d) reacts with 0.5 equivalents of alkylating reagent giving the trichloro methyl compound [Ta{η5-C5H3(SiMe3)2}Cl3Me] (10) in good yield. On the other hand, [Ta{η5-C5H3(SiMe3)2}Cl4] (1d) reacts with 2 equivalents of MgClMe in hexane at room temperature giving a mixture of dichloro dimethyl and chloro trimethyl complexes[Ta{η5-C5H3(SiMe3)2}Cl4−xMex] (x = 2, 11; 3, 12), while the use of 4 equivalents of MgClMe converts 1c into the tetramethyl derivative [Ta{η5-C5H3(SiClMe2)(SiMe3)}Me4] (13). Finally, a tetramethyl tantalum complex [Ta{η5-C5H3(SiMe3)2}Me4] (14) was prepared by reaction of [Ta{η5-C5H3(SiXMe2)(SiMe3)}Cl4] (X = Cl, 1c; Me, 1d) with 5 (X = Cl) or 4 (X = Me) equivalents of MgClMe in diethyl ether (X = Cl) or hexane (X = Me), respectively, as solvent. All the complexes were studied by IR and NMR spectroscopy and the molecular structure of the complex 11 was determined by X-ray diffraction methods. 相似文献
15.
Yongyong Wu Changtao Qian Enhong Sheng Gaosheng Yang Lijun Zhang 《Journal of organometallic chemistry》2005,690(18):4139-4149
A series of new organolanthanide(II) complexes with furfuryl- and tetrahydrofurfuryl-functionalized indenyl ligands were synthesized via one-electron reductive elimination reaction. Treatments of [(Me3Si)2N]3LnIII(μ-Cl)Li(THF)3 (Ln = Yb, Eu) with 2 equiv. of C4H7OCH2C9H7 (1) or C4H3OCH2C9H7 (2), respectively in toluene at moderate high temperatures produced, after workup, the corresponding organolanthanide(II) complexes with formula [η5:η1-(C4H7OCH2C9H6)]2LnII (Ln = Yb (5), Ln = Eu (6)) and [η5:η1-(C4H3OCH2C9H6)]2LnII (Ln = Yb (7), Ln = Eu (8)) in reasonable to good yields. Treatments of [(Me3Si)2N]3LnIII(μ-Cl)Li(THF)3 (Ln = Yb, Eu) with 2 equiv. of C4H7OCH2C9H6SiMe3 (3) or C4H3OCH2C9H6SiMe3 (4), respectively, in toluene at moderate high temperatures afforded, after workup, the corresponding organolanthanide(II) complexes with formula [η5:η1-(C4H7OCH2C9H5SiMe3)]2LnII (Ln = Yb (9), Ln = Eu (10)) and[η5:η1-(C4H3OCH2C9H5SiMe3)]2LnII (Ln = Yb (11), Ln = Eu (12)) in good to high yields. All the compounds were fully characterized by spectroscopic methods and elemental analyses. The structure of complex 9 was additionally determined by single-crystal X-ray analyses. Studies on the catalytic activities of complexes showed that the complexes having silyl group functionalized indenyl ligands have high catalytic activities on ε-caprolactone polymerization. The temperatures, substituted groups on the indenyl ligands of the complexes, and solvents effects on the catalytic activities of the complexes were examined. 相似文献
16.
M.C. Torralba J.A. Campo E. Pinilla M.R. Torres 《Journal of organometallic chemistry》2006,691(4):765-778
Two types of Pd-complexes containing the new N,N′-ligands 2-[3-(4-alkyloxyphenyl)pyrazol-1-yl]pyridine (pzRpy; R = C6H4OCnH2n+1, n = 6 (hp), 10 (dp), 12 (ddp), 14 (tdp), 16 (hdp), 18 (odp)) (1-6), namely c-[Pd(Cl)2(pzRpy)] (7-10) and c-[Pd(η3-C3H5)(pzRpy)]BF4 (11-16), have been synthesised and characterised by different spectroscopic techniques. Those members of the second type containing the largest chains (R = ddp 13, tdp 14, hdp 15, odp 16) have been found to have liquid crystal properties showing smectic A mesophases. By contrast, neither the free ligands pzRpy nor their related c-[Pd(Cl)2(pzRpy)] complexes exhibited mesomorphism. The new synthesised metallomesogens are mononuclear complexes with an unsymmetrical molecular shape as deduced from the X-ray structures of c-[Pd(η3-C3H5)(pzRpy)]BF4 (R = hp, 11; dp, 12). Both compounds, which are isostructural, show a distorted square-planar environment on the palladium centres defined by the allyl and the bidentate pzRpy ligands. The crystal structure reveals that both the counteranion and the pzRpy ligand function as a source of hydrogen-bonding and intermolecular π?π contacts resulting in a 2D supramolecular assembly. 相似文献
17.
Alexander Hildebrandt 《Journal of organometallic chemistry》2011,696(20):3231-3237
The synthesis and properties of heterobimetallic Ti-M complexes of type {[[Ti](μ-η1:η2-CCSiMe3)][M(μ-η1:η2-CCSiMe3)(CO)4]} (M = Mo: 5, [Ti] = (η5-C5H5)2Ti; 6, [Ti] = (η5-C5H4SiMe3)2Ti; M = W: 7, [Ti] = (η5-C5H5)2Ti; 8, [Ti] = (η5-C5H4SiMe3)2Ti) and {[Ti](μ-η1:η2-CCSiMe3)2}MO2 (M = Mo: 13, [Ti] = (η5-C5H5)2Ti; 14, [Ti] = (η5-C5H4SiMe3)2Ti). M = W: 15, [Ti] = (η5-C5H5)2Ti; 16, [Ti] = (η5-C5H4SiMe3)2Ti) are reported. Compounds 5-8 were accessible by treatment of [Ti](CCSiMe3)2 (1, [Ti] = (η5-C5H5)2Ti; 2, [Ti] = (η5-C5H4SiMe3)2Ti) with [M(CO)5(thf)] (3, M = Mo; 4, M = W) or [M(CO)4(nbd)] (9, M = Mo; 10, M = W; nbd = bicyclo[2.2.1]hepta-2,5-diene), while 13-16 could be obtained either by the subsequent reaction of 1 and 2 with [M(CO)3(MeCN)3] (11, M = Mo; 12, M = W) and oxygen, or directly by oxidation of 5-8 with air. A mechanism for the formation of 5-8 is postulated based on the in-situ generation of [Ti](CCSiMe3)((η2-CCSiMe3)M(CO)5), {[Ti](μ-η1:η2-CCSiMe3)2}-M(CO)4, and [Ti](μ-η1:η2-CCSiMe3)((μ-CCSiMe3)M(CO)4) as a result of the chelating effect exerted by the bis(alkynyl) titanocene fragment and the steric constraints imposed by the M(CO)4 entity.The molecular structure of 5 in the solid state were determined by single crystal X-ray diffraction analysis. In doubly alkynyl-bridged 5 the alkynides are bridging the metals Ti and Mo as a σ-donor to one metal and as a π-donor to the other with the [Ti](CCSiMe3)2Mo core being planar. 相似文献
18.
Wendy Rusli Boon-Ying Tay Ludger P. Stubbs Martin van Meurs Jozel Tan Chacko Jacob Sze-Chen Chia Yuan-Ling Woo Cun Wang 《Journal of organometallic chemistry》2011,696(11-12):2414-2419
A styrene unit has been successfully incorporated into the half metallocene constrained-geometry framework as [(η5-C5Me4)SiMe2(η1-NC6H4CHCH2)]MX2 (M = Ti, X = NMe2, 6a; M = Zr, X = NMe2, 6b; M = Ti, X = Cl, 7a; M = Zr, X = Cl, 7b). These complexes have been characterized with 1H NMR, 13C NMR spectroscopy together with single crystal X-ray diffraction studies of 6a and 6b. A polystyrene-immobilized constrained-geometry catalyst 8 was formed by the radical copolymerization of 7a with styrene using AIBN as the initiator. The complexes 6a, 6b, 7a and 8 gave active homogeneous catalysts for the copolymerization of ethylene with 1-octene when treated with excess methylalumoxane (MAO). The polymerization results showed that 7a was highly active and effective for the incorporation of comonomer 1-octene whereas the zirconium complex 6b and the immobilized catalyst 8 yield low activities and low incorporations of 1-octene in the products with broad molecular weight distributions. 相似文献
19.
Maravanji S. Balakrishna P. Chandrasekaran Ramalingam Venkateswaran 《Journal of organometallic chemistry》2007,692(13):2642-2648
Cyclodiphosphazanes having donor functionalities such as cis-[tBuNP(OR)]2 (R = C6H4OMe-o (2); R = CH2CH2OMe (3); R = CH2CH2SMe (4); R = CH2CH2NMe2 (5)) were obtained in good yield by reacting cis-[tBuNPCl]2 (1) with corresponding nucleophiles. The reactions of 2-5 with [RuCl2(η6-cymene)]2, [MCl(COD)]2 (M = Rh, Ir), [PdCl2(PEt3)]2 and [MCl2(COD)] (M=Pd, Pt) result in the formation of exclusively monocoordinated mononuclear complexes of the type cis-[{tBuNP(OR)}2MLn-κP] irrespective of the reaction stoichiometry and the reaction conditions. In contrast, 2-5 react with [RhCl(CO)2]2, [PdCl(η3-C3H5)]2, CuX (X=Cl, Br, I) to give homobinuclear complexes. Interestingly, CuX produces both mono and binuclear complexes depending on the stoichiometry of the reactants and the reaction conditions. The mononuclear complexes on treatment with appropriate metal reagents furnish heterometallic complexes. 相似文献
20.
Aline Maisse-François Laurine Azor Anne-Laure Schmitt Ariane Coquel Lydia Brelot Richard Welter Stéphane Bellemin-Laponnaz Samuel Dagorne 《Journal of organometallic chemistry》2012,696(26):4248-4256
The present contribution describes the synthesis and structural characterization of structurally diverse organoaluminum species supported by variously substituted aminophenolate-type ligands: these Al complexes are all derived from the reaction of AlMe3 with aminophenols 2-CH2NH(R)-C6H3OH (1a, R = mesityl (Mes); 1b, R = 2,6-di-isopropylphenyl (Diip)) and 2-CH2NH(R)-4,6-tBu2-C6H2OH (1c, R = Mes; 1d, R = Diip). The low temperature reaction of AlMe3 with 1a–b readily affords the corresponding Al dimeric species [μ-η1,η1-N,O-{2-CH2NH(R)-C6H4O}]2Al2Me4 (2a–b), consisting of twelve-membered ring aluminacycles with two μ-η1,η1-N,O-aminophenolate units, as determined by X-ray crystallographic studies. Heating a toluene solution of 2a (80 °C, 3 h) affords the quantitative and direct formation of the dinuclear aluminium complex Al[η2-N; μ,η2-O-{2-CH2N(Mes)-C6H4O}](AlMe2) (4a) while species 2b, under the aforementioned conditions, affords the formation of the Al dimeric species [η2-N,O-{2-CH2N(Dipp)-C6H4O}AlMe]2 (3b), as deduced from X-ray crystallography for both 3b and 4a. In contrast, the reaction of bulky aminophenol pro-ligands 1c–d with AlMe3 afford the corresponding monomeric Al aminophenolate chelate complexes η2-N,O-{2-CH2NH(R)-4,6-tBu2-C6H2O}AlMe2 (5c–d; R = Mes, Diip; Scheme 3) as confirmed by X-ray crystallographic analysis in the case of 5d. Subsequent heating of species 5c–d yields, via a methane elimination route, the corresponding Al-THF amido species η2-N,O-{2-CH2N(R)-4,6-tBu2-C6H2O}Al(Me)(THF) (6c–d; R = Mes, Diip). Compounds 6c–6d, which are of the type {X2}Al(R)(L) (L labile), may well be useful as novel well-defined Lewis acid species of potential use for various chemical transformations. Overall, the sterics of the aminophenol backbone and, to a lesser extent, the reaction conditions that are used for a given ligand/AlMe3 set essentially govern the rather diverse “structural” outcome in these reactions, with a preference toward the formation of mononuclear Al species (i.e. species 5c–d and 6c–d) as the steric demand of the chelating N,O-ligand increases. 相似文献