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1.
The diiron complexes [Fe(Cp)(CO){μ-η2:η2-C[N(Me)(R)]NC(C6H3R′)CCH(Tol)}Fe(Cp)(CO)] (R = Xyl, R′ = H, 3a; R = Xyl, R′ = Br, 3b; R = Xyl, R′ = OMe, 3c; R = Xyl, R′ = CO2Me, 3d; R = Xyl, R′ = CF3, 3e; R = Me, R′ = H, 3f; R = Me, R′ = CF3, 3g) are obtained in good yields from the reaction of [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)(p-NCC6H4R′)(Cp)2]+ (R = Xyl, R′ = H, 2a; R = Xyl, R′ = Br, 2b; R = Xyl, R′ = OMe, 2c; R = Xyl, R′ = CO2Me, 2d; R = Xyl, R′ = CF3, 2e; R = Me, R′ = H, 2f; R = Me, R′ = CF3, 2g) with TolCCLi. The formation of 3 involves addition of the acetylide at the coordinated nitrile and C-N coupling with the bridging aminocarbyne together with orthometallation of the p-substituted aromatic ring and breaking of the Fe-Fe bond. Complexes 3a-e which contain the N(Me)(Xyl) group exist in solution as mixtures of the E-trans and Z-trans isomers, whereas the compounds 3f,g, which posses an exocyclic NMe2 group, exist only in the Z-cis form. The crystal structures of Z-trans-3b, E-trans-3c, Z-trans-3e and Z-cis-3g have been determined by X-ray diffraction experiments. 相似文献
2.
Stephanie K HurstTong Ren 《Journal of organometallic chemistry》2002,660(1):1-5
The reactions between Ru2(ap)4Cl and the appropriate lithiated aryl acetylene resulted in the complexes Ru2(ap)4(CC4-C6H4CCX) with X as SiMe3 (1), H (2) and Ru2(ap)4 (3), 1,3-[Ru2(ap)4(CC)]2(C6H4) (4), 1,3-[{Ru2(ap)4(CC)}2]C6H35-CCH (5) and 1-[Ru2(ap)4(CC)]C6H33,5-(CCH)2 (6), where ap is 2-anilinopyridinate. The spectroscopic and electrochemical properties of the new complexes have been assessed. Complexes 3, 4 and 6 display two-electron oxidation and reductions, implying the absence of any significant electronic interaction between the two Ru2(ap)4 units in these complexes. 相似文献
3.
A new series of thermally stable group 10 platinum(II) and group 12 mercury(II) poly-yne polymers containing biphenyl spacer trans-[-Pt(PBu3)2CC(p-C6H4)2CC-]n and [HgCC(p-C6H4)2CC-]n were prepared in good yields by Hagihara’s dehydrohalogenation reaction of the corresponding metal chloride precursors with 4,4′-diethynylbiphenyl HCC(p-C6H4)2CCH at room temperature. We report the optical spectroscopy of these polymetallaynes and compare the results with their bimetallic model complexes trans-[Pt(Ph)(PEt3)2CC(p-C6H4)2CCPt(Ph)(PEt3)2] and [MeHgCC(p-C6H4)2CCHgMe] as well as the group 11 gold(I) counterpart [(PPh3)AuCC(p-C6H4)2CCAu(PPh3)]. The structural properties of all model complexes have been studied by X-ray crystallography. The influence of the heavy metal atom in these metal alkynyl systems on the intersystem crossing rate and the spatial extent of lowest singlet and triplet excitons is systematically characterized. Our investigations indicate that the organic triplet emissions can be harvested by the heavy-atom effect of group 10-12 transition metals (viz., Pt, Au, and Hg) which enables efficient intersystem crossing from the S1 singlet excited state to the T1 triplet excited state. 相似文献
4.
The reaction of aryl acetylide anions with phenyl isocyanate and subsequent addition of a protonating agent such as ethanol affords good yields of 3-aminomaleimides, formed by the cyclization of one molecule of alkyne with two isocyanates. When the reaction is quenched with water instead, cyclopentadienone imines are formed as the major products. 相似文献
5.
Pradep Mathur Anjan K. Bhunia Ch. Srinivasu Shaikh Md. Mobin 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4-5):899-901
Group 16 elements serve as useful bridging and stabilising single atom ligands in mixed-metal carbonyl complexes and impart unusual reactivity on coordinated acetylenic moieties. Reactions of [Fe 3 (CO) 9 (μ 3 -E) 2 ] (E = S, or Se) with mononuclear acetylide complexes, [CpM(CO)_3-x(CCR)] (M = Mo or W, x = 0, R = Ph; M = Fe, x = 1, R = Ph or ferrocenyl) under facile conditions yield complexes featuring acetylide coupling, acetylide-flip and formation of oxo and acetylide-bridged complexes. In presence of free acetylenes, unusual ligand systems arising from C─S bond formation are observed and under certain conditions, formation of quinones by coupling of acetylenes with carbon monoxide is facilitated. 相似文献
6.
The trans-palladium bis(σ-acetylide) complex (Et3P)2Pd(C30H12) (2) was synthesized from hexane 4 in 77% yield via a simple three-step process. The X-ray crystal structure of 2 shows a strained and warped annulenic core upon insertion of the organometallic fragment. UV-vis data of the molecule suggest limited electronic delocalization throughout the metallacycle. 相似文献
7.
8.
Sascha Dietrich 《Journal of organometallic chemistry》2011,696(13):2491-2498
The synthesis and properties of heterobimetallic Ti-Cd complexes of type {[Ti](μ-η1:η2-CCR)2}CdX2 ([Ti] = Ti(η5-C5H4SiMe3)2; R = SiMe3: 3a, X = Cl; 3b, X = Br; 3c, X = I; R = Fc: 3d, X = Br; Fc = Fe(η5-C5H4)(η5-C5H5) is reported. These compounds were accessible by treatment of [Ti](CCR)2 (1a, R = SiMe3; 1b, R = Fc) with the cadmium salts CdX2 (2a, X = Cl; 2b, X = Br; 2c, X = I) in a 1:1 M ratio in diethyl ether. Dissolving, for example, 3b in tetrahydrofuran afforded coordination polymer [Cd(μ-Br)2(thf)2]n (4) along with the tweezer molecule 1a. Treatment of 3b with two equiv of LiCCFc (5) gave {[Ti](μ-η1:η2-CCSiMe3)2}Cd(CCFc)2 (6) which eliminated at ambient temperature the all-carbon buta-1,3-diyne FcCC-CCFc (7) producing 1a and elemental Cd. The same reaction behavior was observed, when 2b was reacted with 5. The thus obtained bis(alkynyl) cadmium complex Cd(CCFc)2 (8) is redox-active at low temperature producing 7 and Cd(0). When mercury halides HgX2 (9a, X = Cl; 9b, X = Br) are used, then the titanocene dihalides [Ti]X2 (10a, X = Cl; 10b, X = Br) together with Me3SiCC-CCSiMe3 (11) and Hg(0) were formed. Nevertheless, mercury acetylides were available by treatment of Hg(OAc)2 (12) with HCCFc (13) in a 1:2 M ratio. Thus obtained Hg(CCFc)2 (14) gave with [CuBr] (15) coordination polymer [{Hg(η2-CCFc)2}(Cu2(μ-Br)2]n (16), while with [AgPF6] oxidation of the ferrocenyl moieties took place affording dicationic [Hg(CCFc)2]2+ (18).The structures of 3b and 4 in the solid state are reported. Compound 3b shows the typical characteristics for heterobimetallic organometallic π-tweezer complexes with cadmium in a tetrahedral environment, while 4 corresponds to a one-dimensional coordination polymer in which the Cd(II) ions are linked in a edge-sharing fashion by bromide bridges in the pseudo-equatorial plane. The appropriate tetrahydrofuran molecules are completing the pseudo-octahedral coordination sphere at cadmium.The cyclic voltammogram of 14 is reported showing a single reversible redox event at E0 = 0.108 V with ΔEp = 76 mV indicating that there is no communication between the Fc termini along the mercury acetylide unit. 相似文献
9.
Jonathan Guild Michael J. Morris Craig C. Robertson Alexander W.H. Speed 《Tetrahedron letters》2019,60(39):151079
The reaction of phenyl acetylide anion with aryl isocyanates followed by quenching with water is shown to produce pyrrolopyrrole (iso-DPP) derivatives in addition to the isomeric cyclopentadienone imines previously reported. If the reaction is quenched with dilute HCl, 5-ylidenepyrrol-2(5H)-ones, formed by a Meyer-Schuster rearrangement, can be isolated instead. A possible mechanism for this reaction is suggested. 相似文献
10.
Two carbon-rich starburst gold(I) acetylide complexes [TEE][Au(PCy3)]4 (3, [TEE]H4=tetraethynylethene) and [TEB][Au(PCy3)]3 (6, [TEB]H3=1,3,5-triethynylbenzene) were prepared and their UV–vis absorption, emission and excitation spectra have been recorded. In fluid CH2Cl2 solutions, 3 exhibits prompt 1(ππ*) fluorescence with λ0–0 and λmax at 413 and 428 nm, respectively, while 6 displays 3(ππ*) phosphorescence with λ0–0 and λmax at 446 and 479 nm, respectively. The crystal structure of 3·CH2Cl2 has been determined. 相似文献