共查询到20条相似文献,搜索用时 31 毫秒
1.
Luigi Busetto 《Journal of organometallic chemistry》2010,695(23):2519-2525
The μ-aminocarbyne complexes [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)(NCMe)(Cp)2][SO3CF3] (R = Me, 1a; Xyl, 1b; Xyl = 2,6-Me2C6H3) react with ethynylferrocene to give the corresponding bridging vinyliminium complexes [Fe2{μ-η1:η3-CN(Me)(R)CHC(Fc)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = Me, 2a; R = Xyl, 2b). Insertion of the ethynylferrocene in the metal-carbyne bond is regiospecific, and leads to the formation of only one isomer.Complexes 2a and 2b undergo hydride addition (by NaBH4) affording the enaminoalkylidene complex [Fe2{μ-η1:η3-C(H)(N(Me)2)CHC(Fc)}(μ-CO)(CO)(Cp)2] (3a) and the bis-alkylidene [Fe2{μ-η1:η2-C(N(Me)(Xyl))CH2C(Fc)}(μ-CO)(CO)(Cp)2] (3b), respectively. Upon treatment with NaH, compounds 2a and 2b undergo fragmentation, affording the 1-metalla-2-aminocyclopenta-1,3-dien-5-one complexes [Fe(CO)(Cp){C(N(Me)(R))}CHC(Fc)C(O)}] (R = Me, 4a; R = Xyl, 4b).The molecular structures of 2b, 3b and 4b have been determined by X-ray diffraction studies. 相似文献
2.
Mohammad El-khateeb Khaled Shawakfeh Heinrich Lang 《Journal of organometallic chemistry》2006,691(18):3743-3748
The hydrosulfido complexes CpRu(L)(L′)SH react with one equivalent of O-alkyl oxalyl chlorides (ROCOCOCl) to form the corresponding O-alkylthiooxalate complexes CpRu(L)(L′)SCOCO2R (L = L′ = PPh3 (1), (2); L = PPh3, L′ = CO (3); R = Me (a), Et (b)). The reactions of the hydrosulfido complexes with half equivalent of oxalyl chloride produce the bimetallic complexes [CpRu(L)(L′)SCO]2 (L = L′ = PPh3 (4), (5); L = PPh3, L′ = CO (6)). The crystal structures of CpRu(PPh3)2SCOCO2Me (1a) and CpRu(dppe)SCOCO2Et (2b) are reported. 相似文献
3.
Wanda Ziemkowska Szymon Kucharski Romana Anulewicz-Ostrowska 《Journal of organometallic chemistry》2004,689(18):2930-2939
1,1,2,2-Tetraphenylethane-1,2-diol (benzopinacole) reacts with R3Al to yield the trinuclear complexes {R5Al3[OC(C6H5)2C(C6H5)2O]2} [where R = Me (1), R = Et (2)]. Reactions of compounds 1 and 2 with water results in an elimination of R3Al and formation of unusual binuclear products {R2Al2(THF)[OC(C6H5)2C(C6H5)2O]2} [3 (R = Me), 4 (R = Et)] and a complicated mixture of R3Al hydrolysis products. Compounds were characterised by spectroscopy and crystal structures of 1-3 have been determined by single crystal X-ray diffraction. Binuclear complexes 3 and 4 demonstrate efficient catalytic activity toward ring-opening polymerisation of ε-caprolactone. 相似文献
4.
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
5.
Luigi Busetto 《Journal of organometallic chemistry》2006,691(11):2424-2439
Primary alkynes R′CCH [R′ = Me3Si, Tol, CH2OH, CO2Me, (CH2)4CCH, Me] insert into the metal-carbon bond of diruthenium μ-aminocarbynes [Ru2{μ-CN(Me)(R)}(μ-CO)(CO)(MeCN)(Cp)2][SO3CF3] [R = 2,6-Me2C6H3 (Xyl), 1a; CH2Ph (Bz), 1b; Me, 1c] to give the vinyliminium complexes [Ru2{μ-η1:η3-C(R′)CHCN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] [R = Xyl, R′ = Me3Si, 2a; R = Bz, R′ = Me3Si, 2b; R = Me, R′ = Me3Si, 2c; R = Xyl, R′ = Tol, 3a; R = Bz, R′ = Tol, 3b; R = Bz, R′ = CH2OH, 4; R = Bz, R′ = CO2Me, 5a; R = Me, R′ = CO2Me, 5b; R = Xyl, R′ = (CH2)4CCH, 6; R = Xyl, R′ = Me, 7a; R = Bz, R′ = Me, 7b; R = Me, R′ = Me, 7c]. The related compound [Ru2{μ-η1:η3-C[C(Me)CH2]CHCN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3], (9) is better prepared by reacting [Ru2{μ-CN(Me)(Xyl)}(μ-CO)(CO)(Cl)(Cp)2] (8) with AgSO3CF3 in the presence of HCCC(Me)CH2 in CH2Cl2 at low temperature.In a similar way, also secondary alkynes can be inserted to give the new complexes [Ru2{μ-η1:η3-C(R′)C(R′)CN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = Bz, R′ = CO2Me, 11; R = Xyl, R′ = Et, 12a; R = Bz, R′ = Et, 12b; R = Xyl, R′ = Me, 13). The reactions of 2-7, 9, 11-13 with hydrides (i.e., NaBH4, NaH) have been also studied, affording μ-vinylalkylidene complexes [Ru2{μ-η1:η3-C(R′)C(R″)C(H)N(Me)(R)}(μ-CO)(CO)(Cp)2] (R = Bz, R′ = Me3Si, R″ = H, 14a; R = Me, R′ = Me3Si, R″ = H, 14b; R = Bz, R′ = Tol, R″ = H, 15; R = Bz, R′ = R″ = Et, 16), bis-alkylidene complexes [Ru2{μ-η1:η2-C(R′)C(H)(R″)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (R′ = Me3Si, R″ = H, 17; R′ = R″ = Et, 18), acetylide compounds [Ru2{μ-CN(Me)(R)}(μ-CO)(CO)(CCR′)(Cp)2] (R = Xyl, R′ = Tol, 19; R = Bz, R′ = Me3Si, 20; R = Xyl, R′ = Me, 21) or the tetranuclear species [Ru2{μ-η1:η2-C(Me)CCN(Me)(Bz)}(μ-CO)(CO)(Cp)2]2 (23) depending on the properties of the hydride and the substituents on the complex. Chromatography of 21 on alumina results in its conversion into [Ru2{μ-η3:η1-C[N(Me)(Xyl)]C(H)CCH2}(μ-CO)(CO)(Cp)2] (22). The crystal structures of 2a[CF3SO3] · 0.5CH2Cl2, 12a[CF3SO3] and 22 have been determined by X-ray diffraction studies. 相似文献
6.
A terminally coordinated CO ligand in the complexes [Fe2{μ-CN(Me)R}(μ-CO)(CO)2(Cp)2][SO3CF3] (R = Me, 1a; R = Xyl, 1b; Xyl = 2,6-Me2C6H3), is readily displaced by primary and secondary amines (L), in the presence of Me3NO, affording the complexes [Fe2{μ-CN(Me)R}(μ-CO)(CO)(L)(Cp)2][SO3CF3] (R = Me, L = NH2Et, 4a; R = Xyl, L = NH2Et, 4b; R = Me, L = NH2Pri, 5a; R = Xyl, L = NH2Pri, 5b; R = Xyl, L = NH2C6H11, 6; R = Xyl, L = NH2Ph, 7; R = Xyl, L = NH3, 8; R = Me, L = NHMe2, 9a; R = Xyl, L = NHMe2, 9b; R = Xyl, = NH(CH2)5, 10). In the absence of Me3NO, NH2Et gives addition at the CO ligand of 1b, yielding [Fe2{μ-CN(Me)(Xyl)}(μ-CO)(CO){C(O)NHEt}(Cp)2] (11). Carbonyl replacement is also observed in the reaction of 1a-b with pyridine and benzophenone imine, affording [Fe2{μ-CN(Me)R}(μ-CO)(CO)(L)(Cp)2][SO3CF3] (R = Me, L = Py, 12a; R = Xyl, L = Py, 12b; R = Me, L = HNCPh2, 13a; R = Xyl, L = HNCPh2, 13b). The imino complex 13b reacts with p-tolylacetylide leading to the formation of the μ-vinylidene-diaminocarbene compound [Fe2{μ-η1:η2- CC(Tol)C(Ph)2N(H)CN(Me)(Xyl){(μ-CO)(CO)(Cp2)] (15) which has been studied by X-ray diffraction. 相似文献
7.
The synthesis and the characterization of some new aluminum complexes with bidentate 2-pyrazol-1-yl-ethenolate ligands are described. 2-(3,5-Disubstituted pyrazol-1-yl)-1-phenylethanones, 1-PhC(O)CH2-3,5-R2C3HN2 (1a, R = Me; 1b, R = But), were prepared by solventless reaction of 3,5-dimethyl pyrazole or 3,5-di-tert-butyl pyrazole with PhC(O)CH2Br. Reaction of 1a or 1b with (R1 = Me, Et) yielded N,O-chelate alkylaluminum complexes (2a, R = R1 = Me; 2b, R = But, R1 = Me; 2c, R = Me, R1 = Et). Compound 1a was readily lithiated with LiBun in thf or toluene to give lithiated species 3. Treatment of 3 with 0.5 equiv of MeAlCl2 or AlCl3 yielded five-coordinated aluminum complexes [XAl(OC(Ph)CH{(3,5-Me2C3HN2)-1})2] (4, X = Me; 5, X = Cl). Reaction of 5 with an equiv of LiHBEt3 generated [Al(OC(Ph)CH{(3,5-Me2C3HN2)-1})3] (6). Complex 6 was also obtained by reaction of 3 with 1/3 equiv of AlCl3. Treatment of 5 with 2 equiv of AlMe3 yielded complex 2a, whereas with an equiv of AlMe3 afforded a mixture of 2a and [Me(Cl)AlOC(Ph)CH{(3,5-Me2C3HN2)-1}] (7). Compounds 1a, 1b, 2a-2c and 4-6 were characterized by elemental analyses, NMR and IR (for 1a and 1b) spectroscopy. The structures of complexes 2a and 5 were determined by single crystal X-ray diffraction techniques. Both 2a and 5 are monomeric in the solid state. The coordination geometries of the aluminum atoms are a distorted tetrahedron for 2a or a distorted trigonal bipyramid for 5. 相似文献
8.
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
9.
Luigi Busetto Mauro Salmi Valerio Zanotti 《Journal of organometallic chemistry》2007,692(11):2245-2252
The bridging diiron thiocarbyne complex [Fe2{μ-CS(Me)}(μ-CO)(CO)2(Cp)2][SO3CF3] (1) reacts with activated olefins (methyl acrylate, acrylonitrile, styrene, diethyl maleate), in the presence of Me3NO and NaH, to give the corresponding μ-allylidene complexes [Fe2{μ-η1:η3-Cα(SMe)Cβ(R′)Cγ(H)(R″)} (μ-CO)(CO)(Cp)2] (R″ = CO2Me, R′ = H, 3a; R″ = CN, R′ = H, 3b; R″ = C6H5, R′ = H, 3c; R″ = R′ = CO2Et, 3d). The coupling reaction of olefin with thiocarbyne is regio- and stereospecific, leading to the formation of only one isomer. C-C bond formation occurs between the less substituted alkene carbon and the thiocarbyne. Moreover, olefinic hydrogens of the bridging ligands are mutually trans.The reactions of 3a-b with MeSO3CF3 result, selectively, in the formation of the cationic μ-sulphonium allylidene complexes [Fe2{μ-η1:η3-Cα(SMe2)Cβ (H)Cγ(H)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = CO2Me, 4a; R = CN, 4b). Compound 4a undergoes displacement of the SMe2 group by nucleophiles such as NaBH4, NBu4CN and NaOMe, affording the complexes [Fe2{μ-η1:η3-Cα(R)Cβ (H)Cγ(H)(CO2Me)}(μ-CO)(CO)(Cp)2] (R = H, 5a; R = CN, 5b; R = OMe, 5c), respectively. The molecular structures of 3a and 5a have been determined by X-ray diffraction studies. 相似文献
10.
Eight dialkylgallium complexes of type R2GaL [(M = Me, L = 1-(2-pyridyl)methyleneimino-2-naphthonato (1), M = Et, L = 1-(2-pyridyl)methyleneimino-2-naphthonato (2), M = Me, L = 1-phenylmethyleneimino-2-naphthonato (3), M = Et, L = 1-phenylmethyleneimino-2-naphthonato (4), M = Me, L = 1-(p-methoxylphenyl)methyleneimino-2-naphthonato (5), M = Me, L = 1-(3,4-dimethoxylphenyl)methyleneimino-2-naphthonato (6), M = Me, L = 1-naphthylmethyleneimino-2-naphthonato (7), M = Me, L = 1-naphthylmethyleneimino-2-naphthonato (8)) have been synthesized by reaction of trialkylgallium with appropriate 1-arylmethyleneimino-2-naphthols. The complexes have been characterized by elemental analysis, 1H NMR, IR and mass spectrometry. Structure of dimethyl[1-(2-pyridyl)methyleneimino-2-naphthonato]gallium (1) has been determined by X-ray single crystal analysis. Ga atom is five coordinate in the structure. Photoluminescent properties have been measured. The maximum emission wavelengths are in the range of 358 and 412 nm with the intensity of 13-325 a.u. The electroluminescent properties of 3, 5, 7 and 8 have been measured. The maximum emission wavelengths are in the range of 450 and 480 nm. 相似文献
11.
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
12.
Reactions of 0.5 eq. of the dinuclear complexes [(η6-arene)Ru(μ-Cl)Cl]2 (arene = η6-C6H6, η6-p-iPrC6H4Me) and [(Cp∗)M(μ-Cl)Cl]2 (M = Rh, Ir; Cp∗ = η5-C5Me5) with 4,6-disubstituted pyrazolyl-pyrimidine ligands (L) viz. 4,6-bis(pyrazolyl)pyrimidine (L1), 4,6-bis(3-methyl-pyrazolyl)pyrimidine (L2), 4,6-bis(3,5-dimethyl-pyrazolyl)pyrimidine (L3) lead to the formation of the cationic mononuclear complexes [(η6-C6H6)Ru(L)Cl]+ (L = L1, 1; L2, 2; L3, 3), [(η6-p-iPrC6H4Me)Ru(L)Cl]+ (L = L1, 4; L2, 5; L3, 6), [(Cp∗)Rh(L)Cl]+ (L = L1, 7; L2, 8; L3, 9) and [(Cp∗)Ir(L)Cl]+ (L = L1, 10; L2, 11; L3, 12), while reactions with 1.0 eq. of the dinuclear complexes [(η6-arene)Ru(μ-Cl)Cl]2 and [(Cp∗)M(μ-Cl)Cl]2 give rise to the dicationic dinuclear complexes [{(η6-C6H6)RuCl}2(L)]2+ (L = L1, 13; L2, 14; L3, 15), [{(η6-p-iPrC6H4Me)RuCl}2(L)]2+ (L = L1, 16; L2, 17; L3, 18), [{(Cp∗)RhCl}2(L)]2+ (L = L1, 19; L2, 20; L3, 21) and [{(Cp∗)IrCl}2(L)]2+ (L = L1 22; L2, 23; L3 24). The molecular structures of [3]PF6, [6]PF6, [7]PF6 and [18](PF6)2 have been established by single crystal X-ray structure analysis. 相似文献
13.
The neutral arene ruthenium azido complexes [(η6-p-cymene)Ru(LL)(N3)], [LL = acetylacetonato (acac) (4), benzoylacetonato (bzac) (5) diphenylbenzoyl methane (dbzm) (6)] undergo [3+2] cycloaddition reaction with a series of activated alkynes and fumaronitrile to produce the arene ruthenium triazolato complexes: [(η6-p-cymene)Ru(LL){N3C2(CO2R)2}] [LL = (acac), R = Me (7); LL = (bzac), R = Me (8); LL = (dbzm), R = Me (9); LL = (acac), R = Et (10); LL = (bzac), R = Et (11); LL = (dbzm), R = Et (12) and [(η6-p-cymene)Ru(LL)(N3C2HCN)]; LL = acac (13), bzac (14); dbzm (15). However, cationic azido complexes, [(η6-p-cymene)Ru(dppe)(N3)]+ and [(η6-p-cymene)Ru(dppm)(N3)]+ do not undergo such cycloaddition reactions. The complexes were characterized on the basis of microanalyses, FT-IR and NMR spectroscopic data. Crystal structures of representative complexes were determined by single crystal X-ray diffraction. 相似文献
14.
Prithwiraj Byabartta 《高等学校化学研究》2008,24(2):180-186
A variety of gold(Ⅲ) adducts having a-ligated oxygen-donor ligands have been prepared from [Au(ppy)Cl2](ppy.phenylpyridine)(1) either by partial or total replacement of the chloride ions. The new species comprise hydroxo-[Au(ppy)(OH)Cl](2), and [Au(ppy)(OH)2](3), oxo-[Au2(ppy)2(μ-O)2](4), acetate-[Au(ppy)(O2CMe2)] (5), and alkoxo complexes-[Au(ppy)(OR)Cl](6, 7) and [Au(ppy)(OR)2](8--10)(R=Me, 6 and 8; Et, 7 and 9; Pr, 10). The dihydroxo and the oxo complexes can be interconverted by refluxing the former in anhydrous THF and the latter in water. The hydroxides 2 and 3 and the acetato complex 5 undergo σ-ligand metathesis in ROH solution(R=Me, Et or Pr) to give the corresponding alkoxides. 相似文献
15.
Cheng Zhang 《Journal of organometallic chemistry》2008,693(19):3151-3158
A series of aluminum and zinc complexes supported by functionalized phenolate ligands were synthesized and characterized. Reaction of 2-(3,5-R2C3N2)C6H4NH2 (R = Me, Ph) with salicylaldehyde or 3,5-di-tert-butylsalicylaldehyde afforded 2-((2-(1H-pyrazol-1-yl)phenylimino)methyl)phenol derivatives 2a-2d. Treatment of 2a-2d with an equiv. of AlR23 (R2 = Me, Et) gave corresponding aluminum aryloxides 3a-3e, while reaction with an equiv. of ZnEt2 afforded zinc aryloxides 4a-4d. Treatment of 2c with 0.5 equiv. of ZnEt2 formed diphenolato zinc complex 5. All new compounds were characterized by 1H and 13C NMR spectroscopy and elemental analyses. The structures of complexes 3a, 4a and 5 were further characterized by single crystal X-ray diffraction techniques. The catalytic activity of complexes 3-5 toward the ring-opening polymerization of ε-caprolactone was studied. The zinc complexes (4a-4d) exhibited higher catalytic activity than the aluminum complexes (3a-3e). The diphenolato zinc complex 5 showed lower catalytic activity than the ethylzinc complexes 4a-4d. The aluminum complex (3b) is inactive to initiate the ROP of rac-lactide, while the zinc complex (4d) is active initiator for the ROP of rac-lactide, giving atactic polylactide. 相似文献
16.
Luigi Busetto 《Journal of organometallic chemistry》2008,693(1):57-67
The bridging aminocarbyne complexes [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)2(Cp)2][SO3CF3] (R = Me, 1a; Xyl, 1b; 4-C6H4OMe, 1c; Xyl = 2,6-Me2C6 H3) react with acrylonitrile or methyl acrylate, in the presence of Me3NO and NaH, to give the corresponding μ-allylidene complexes [Fe2{μ-η1:η3- Cα(N(Me)(R))Cβ(H)Cγ(H)(R′)}(μ-CO)(CO)(Cp)2] (R = Me, R′ = CN, 3a; R = Xyl, R′ = CN, 3b; R = 4-C6H4OMe, R′ = CN, 3c; R = Me, R′ = CO2Me, 3d; R = 4-C6H4OMe, R′ = CO2Me, 3e). Likewise, 1a reacts with styrene or diethyl maleate, under the same reaction conditions, affording the complexes [Fe2{μ-η1:η3-Cα(NMe2)Cβ(R′)Cγ(H)(R″)}(μ-CO)(CO)(Cp)2] (R′ = H, R″ = C6H5, 3f; R′ = R″ = CO2Et, 3g). The corresponding reactions of [Ru2{μ-CN(Me)(CH2Ph)}(μ-CO)(CO)2(Cp)2][SO3CF3] (1d) with acrylonitrile or methyl acrylate afford the complexes [Ru2{μ-η1:η3-Cα(N(Me)(CH2Ph))Cβ(H)Cγ(H)(R′)}(μ-CO)(CO)(Cp)2] (R′ = CN, 3h; CO2Me, 3i), respectively.The coupling reaction of olefin with the carbyne carbon is regio- and stereospecific, leading to the formation of only one isomer. C-C bond formation occurs selectively between the less substituted alkene carbon and the aminocarbyne, and the Cβ-H, Cγ-H hydrogen atoms are mutually trans.The reactions with acrylonitrile, leading to 3a-c and 3h involve, as intermediate species, the nitrile complexes [M2{μ-CN(Me)(R)}(μ-CO)(CO)(NC-CHCH2)(Cp)2][SO3CF3] (M = Fe, R = Me, 4a; M = Fe, R = Xyl, 4b; M = Fe, R = 4-C6H4OMe, 4c; M = Ru, R = CH2C6H5, 4d).Compounds 3a, 3d and 3f undergo methylation (by CH3SO3CF3) and protonation (by HSO3CF3) at the nitrogen atom, leading to the formation of the cationic complexes [Fe2{μ-η1:η3-Cα(N(Me)3)Cβ(H)Cγ(H)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = CN, 5a; R = CO2Me, 5b; R = C6H5, 5c) and [Fe2{μ-η1:η3-Cα(N(H)(Me)2)Cβ(H)Cγ(H)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = CN, 6a; R = CO2Me, 6b; R = C6H5, 6c), respectively.Complex 3a, adds the fragment [Fe(CO)2(THF)(Cp)]+, through the nitrile functionality of the bridging ligand, leading to the formation of the complex [Fe2{μ-η1:η3-Cα(NMe2)Cβ(H)Cγ(H)(CNFe(CO)2Cp)}(μ-CO)(CO)(Cp)2][SO3CF3] (9).In an analogous reaction, 3a and [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)2(Cp)2][SO3CF3], in the presence of Me3NO, are assembled to give the tetrameric species [Fe2{μ-η1:η3-Cα(NMe2)Cβ(H)Cγ(H)(CN[Fe2{μ- CN(Me)(R)}(μ-CO)(CO)(Cp)2])}(μ-CO)(CO)(Cp)2][SO3CF3] (R = Me, 10a; R = Xyl, 10b; R = 4-C6H4OMe, 10c).The molecular structures of 3a and 3b have been determined by X-ray diffraction studies. 相似文献
17.
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
18.
The interaction of tris(trimethylsilyl) phosphite (TMSO)3P and E-trifluoromethyl-β-alkoxyenones CF3C(O)CHCHOEt and CF3C(O)CHC(OMe)Me yielded mixtures of E-1,2- and Z-1,4-adducts, CF3C(OTMS)[P(O)(OTMS)2]CCH(OAlk)R 2 and CF3(OTMS)CCHCR(OAlk)[P(O)(OTMS)2] 3 where R and Alk = H and Me, or both Me. Conversion of these 1,2-adducts to 1,4-isomers was effected by increased temperature or by exposure to more tris(trimethylsilyl) phosphite. Acid hydrolysis of 2b (R and Alk = Me) gave ketophosphonic acid CF3C(OH)[P(O)(OH)2]CH2COMe in 88% yield, whereas hydrolysis of 2a (R = H and Alk = Et) with KOH in methanol gave CF3C(OH)[P(O)(OK)2]CHCHOEt in 37% yield. Acid hydrolysis of 3a (R = H and Alk = Et) and 3b (R and Alk = Me) gave phosphonic acid CF3C(OH)2CHCHP(O)(OH)2 in 82% yield and trifluoromethylated 1,2λ5σ4-oxaphosphol-3-en. 相似文献
19.
Shota Niibayashi 《Journal of organometallic chemistry》2005,690(2):276-285
A series of titanocene(III) alkoxides L2Ti(III)OR where L = Cp, R = Et(1b), tBu(1a), 2,6-Me2C6H3(1c), 2,6-tBu2-4-Me-C6H2(1d), or L = Cp*, R = Me(2e), tBu(2a), Ph(2f) was synthesized and subjected to reaction with [CpM(CO)3]2 [M = Mo, W], [CpRu(CO)2]2, and Co2(CO)8. The Ti(III) precursors 1a, 1c, 2a, 2e, and 2f reacted with [CpM(CO)3]2 [M = Mo, W] to form heterobimetallic complexes L2Ti(OR)(μ-OC)(CO)2MCp [M = Mo, W], of which Ti and M are linked by an isocarbonyl bridge. Reactions of these Ti(III) complexes with Co2(CO)8 resulted in formation of Ti-Co1 heterobimetallic complexes, from 2a, 2e, or 2f, or Ti-Co3 tetrametallic complexes, Cp2Ti(OtBu)(μ-OC)Co3(CO)9 from 1a, 1b, or 1c. The products were characterized by NMR, IR, and X-ray crystallography. Reaction mechanisms were proposed from these results, in particular, from steric/electronic effects of titanium alkoxides. 相似文献