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1.
YANG Rui-Na XUE Bao-Yu WANG Dong-Mei JIN Dou-Man Henan Institute of Chemistry Zhengzhou Henan ChinaCHEN Jun LI Ming-Xing Department of Chemistry Fudan University Shanghai China 《中国化学》1997,15(1):76-83
At room temperature, dibenzoyl peroxide undergoes oxidative addition reaction with metallic copper powder and pyridine N-oxide (triphenylphosphine oxide or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin) which affords the last products as binuclear copper(II) complexes, [Cu(C5H5NO)-(C6H5COO)2]2(1), [Cu(OPPh3)(C6H5COO)2]2(2) and [Cu(C6H5COO)(C26H2oN2)](3, C26H2oN2 is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin). The structure of the complexes were characterized by elemental analyses, IR spectra, TG-DTA and magnetic property. Crystals(1) are triclinic, space group P1,a=0.92617(36),b=1.06973(17), c=1.08813(29) nm, a=59.60(2)°, β=74.83(3)°,γ=72.80(2)°, V=0.880 nm3, Dc=1.520 g/cm3, Z=1, R=0.044, Rw=0.048, Mr=805.78, 3477 reflections with I > 3σ(I). Each copper(Ⅱ) ion is coordinated by two bridging bidentate benzoate ligands and one pyridine N-oxide or triphenylphosphine oxide to form dimeric binuclear molecules. The structure of the compound(1) shows a clear centre of symmetry. 相似文献
2.
The reactions of (M = Mo, W) with α,α′-p-, m- and o-dichloro-xylenes yielded p-, m- and o-xylyl bridged dinuclear complexes of in high yields. All of such new complexes are stable to air and water, even stable in dilute acids and bases. 相似文献
3.
Kiran Kumar Varma ChakrahariRajendra Singh Dhayal Sundargopal Ghosh 《Polyhedron》2011,30(6):1048-1054
Pyrolysis of an in-situ generated intermediate, produced in the reaction of [Cp∗MoCl4], 1, (Cp∗ = η5-C5Me5) with [LiBH4·THF], with an excess of difuryl ditelluride in toluene at 90 °C yielded syn and anti isomers of [Cp∗Mo(O)(μ-Te)]2 (2, 3) and [Cp∗2Mo2O2(μ-O)(μ-Te)] (4, 5). In a similar fashion, dibenzyl diselenide yielded syn and anti isomers of [Cp∗Mo(O)(μ-Se)]2 (6, 7), along with the known nido-[(Cp∗Mo)2B4H8Se2]. Note that in parallel with 2-7, [(Cp∗Mo)2B5H9] was isolated as the major product in both cases. Compounds 2-7 have been isolated in modest yield as orange to brown crystalline solids. All the new compounds have been characterized in solution by mass, IR, 1H, 13C, 77Se and 125Te NMR spectroscopy, and the structural types were unequivocally established by crystallographic analysis of 2-4 and 7. 相似文献
4.
A number of bridged half-sandwich titanium complexes [η5:η1-2-C5H4CHPh-4-R1-6-R2C6H2O]TiCl2 [R1 = H (5), Me (6), tBu (7, 8); R2 = H (6, 7), tBu (5, 8)] were synthesized from the reaction of their corresponding trimethylsilyl substituted ligand precursors 2-Me3SiC5H4CHPh-4-R1-6-R2C6H2OSiMe3 [R1 = H (1), Me (2), tBu (3, 4); R2 = H (2, 3), tBu (1, 4)] with TiCl4 in hexane. All new complexes were characterized by 1H and 13C NMR spectroscopy. Molecular structures of complexes 5 and 8 were determined by single crystal X-ray diffraction analysis. Upon activation with AliBu3/Ph3CB (C6F5)4, complexes 5-8 exhibit reasonable catalytic activity for ethylene polymerization and copolymerization with 1-hexene, producing polyethylene and poly(ethylene-co-1-hexene) with moderate molecular weights. 相似文献
5.
Sodio C.N. Hsu Yu-Chen Zheng Min-Yuan Hung 《Journal of organometallic chemistry》2008,693(18):3035-3042
The known complexes [Cp2Fe2(μ-SEt)2(MeCN)2](PF6)2 (1) and Cp2Fe2(μ-SEt)2(CN)2 (2) are prepared to investigate their reactivity. The reaction of complex 2 with equimolar amounts of MeOTf yields a monomethylation product [Cp2Fe2(μ-SEt)2(CN)(CNMe)](OTf) (3). Dimethylation of complex 2 by 2 equiv. MeOTf gives a complex [Cp2Fe2(μ-SEt)2(CNMe)2](OTf)2 (4). Complex 1 containing two labile MeCN ligands reacts with several bidentate phosphine ligands, such as dppm, dppa, and dppf, to afford complexes [Cp2Fe2(μ-SEt)2(dppm)](PF6)2 (5), [Cp2Fe2(μ-SEt)2(dppa)](PF6)2 (6), and [Cp2Fe2(μ-SEt)2(dppf)](PF6)2 (7), respectively. The spectroscopic, electrochemical, and reactivity studies of iron-sulfur core complexes are performed. The structures of complexes 1-7 were confirmed by X-ray crystallography. 相似文献
6.
Narjes Khadir Abdeljalil Assoud Mojtaba Bagherzadeh 《Journal of Coordination Chemistry》2016,69(1):103-111
Reaction of the binucleating S-protected ligand precursors 2-(N,N-dimethylthiocarbamato)-5-methylisophthalaldehyde di-2′-hydroxy anil (I) and 2-(N,N-dimethylthiocarbamato)-5-methylisophthalaldehyde di-2′-hydroxy 5′-methyl anil (II) with nickel(II) acetate tetrahydrate in the presence of pyrazole afforded the binuclear nickel(II) complexes [LINi2(pz)] (1) and [LIINi2(pz)] (2), respectively. The complexes have been characterized by routine physicochemical studies as well as by X-ray single crystal structure analysis. In both complexes, Ni(II) ions are doubly bridged by the thiophenolic sulfur of the pentadentate Schiff base ligand and a pyrazolate group. Efficient protocols for the oxidation of sulfides to sulfoxides with high selectivities, catalyzed by binuclear μ-thiophenolato-μ-pyrazolatonickel(II) in the presence of urea hydrogen peroxide (UHP) were explored. We obtained predominantly the monooxygenated product. The resulting products are obtained in good to excellent yields within a reasonable time. 相似文献
7.
A series of novel α,ω-bis(4-methylphenoxy) alkane functionalized cyclen ligands were synthesized by the nucleophilic substitution reaction of 1,4,7-tris(tert-butyloxycarbonyl)-1,4,7,10-tetraazacyclododecane and α,ω-bis(4-bromomethylphenoxy) alkanes. The corresponding dimeric Zn(II)–cyclen complexes were obtained by reaction of these ligands with Zn(ClO4)2·6H2O. Ligands and complexes were characterized by FT-IR, 1H NMR, and elemental analysis. 相似文献
8.
Six new lanthanide complexes, (H3O)[Ln3(H2O)17(α2-As2W17O61)]·nH2O ((1) Ln=CeIII and n≈13; (2) Ln=PrIII and n≈9; (3) Ln=NdIII and n≈14; (4) Ln=SmIII and n≈8; (5) Ln=EuIII and n≈4; (6) Ln=GdIII and n≈7), have been isolated by conventional solution method and characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction. All the complexes are isomorphic and crystallize in the triclinic space group P-1. These complexes are 1D chain-like structures constructed by lanthanide cations and monovacant Dawson-type [α2-As2W17O61]10− polyoxoanions. The striking feature of the structures is that there are three kinds of coordination environments for lanthanide cations, which are responsible for the formation of polymeric structures. Photoluminescence measurements reveal that 4 and 5 exhibit orange and red fluorescent emission at room temperature, respectively. 相似文献
9.
Four novel oxovanadium(IV) binuclear complexes have been synthesized, namely [(VO)2(IPHTA) (L)2SO4 (L denotes 2,2′-bipyridine (bpy); 1,10-phenanthroline (phen); 4,4′-dimethyl-2,2′-bipyridine (Me2bpy) and 5-nitro-1,10-phenanthroline (NO2-phen)), where IPHTA is the isophthalate dianon. Based on elemental analyses, molar conductivity measurements, IR and electronic spectra studies, it is proposed that these complexes have IPHTA-bridged structures and consist of two vanadium(IV) atoms in a square-pyramidal environment. The complexes [(VO)2(IPHTA)(Me2bpy)2]SO4 (1) and [(VO)2(IPHTA)(bpy)2]SO4 (2) were characterized by variable temperature magnetic susceptibility (4–300 K) and the data could be well fitted by the least-squares method to a susceptibility equation derived from the spin Hamiltonian operator, . The exchange integral, J, was found to be −26.8 cm−1 for (1) and −31.0 cm−1 for (2). These results are commensurate with antifferomagnetic interactions between two oxovanadium(IV) ions within each molecule. The influence of different terminal ligands on magnetic interactions between the metals of this kind of complexes is also discussed. 相似文献
10.
Ling Wu Jun Wang CaiFei Zhu YiJi Lin LeiQi Chen Jun Fan Hui Zhang 《中国科学:化学(英文版)》2010,53(6):1255-1260
The oxalato-bridged dicopper(II) complexes [Cu2(μ-ox)(LRR)2(H2O)2(ClO4)2] (1),[Cu2(μ-ox)(LRR)2(CH3COCH3)2(ClO4)2](1a),[Cu2(μ-ox)(LSS)2(H2O)2(ClO4)2] (2) and [Cu2(μ-ox)(LRR)(LSS)2(CH3COCH3)2(ClO4)2] (3) [LRR = (8R,10R)-(-)-[4,5]-pineno2,2′-bipyridine,LSS = (8S,10S)-(+)-[4,5]-pineno-2,2′-bipyridine;ox2= oxalate] were first prepared.A possible mechanism for the formation of the chial dicopper(II) complexes was proposed.Based on elemental analysis,conductance measurement,UV-Vis spectra,CD spectra and X-ray single-crystal diffraction,the oxalato-bridged structures of 1 and 2 were deduced to adopt two Cu(II) ions and the bridged oxalate lying in the nearly same plane.The crystal structures of 1a and 3 reveal that the coordination geometry around each Cu(II) ion is an elongated and distorted octahedron and two axial solvent molecules and two perchlorate ions are anti to each other respectively in both binuclear molecules.The solution CD spectra of 1 and 2 in the visible d-d range show very weak Cotton effects with peaks at 588 and 779 nm,which are approximately of mirror image,suggesting the optical activities may be derived from the vicinal effects of the chiragenic centers at the pinene group of LRR and LSS,respectively.Complex 1 has been characterized by variable-temperature magnetic susceptibility and the data was least-square fitted to the Blenaey-Bowers equation.The exchange integral J was found to be -338.41(4) cm-1,indicating a strong antiferromagnetic interaction between two copper(II) ions. 相似文献
11.
Mi Jin Kim Myung Jin Jung Yeong Joon Kim Ha Kyoung Sung Ju Young Lee Sung Jin Ham Chan Pil Park 《Tetrahedron letters》2018,59(31):2989-2993
The Pd(II) complexes strongly chelated by two β-iminoenolate ligands were easily synthesized in only two steps, and purified based on their sublimable and highly stable property. The Pd(II) complexes anchored on a silica surface showed good catalytic activity in Suzuki-Miyaura reactions (up to 99% yield with 0.05?mol% catalyst). They tolerated a wide range of temperature (rt~110?°C) and various solvents, and could be reused multiple times after simple recovering process. 相似文献
12.
Barquín Montserrat Garmendia María J. González Bellido Víctor 《Transition Metal Chemistry》1999,24(5):584-588
Binuclear complexes [M2Cl4(-bpym)], where M = VO2+, FeII, CoII or CuII and bpym = 2,2-bipyrimidine, and [M2(hfacac)4(-bpym)] complexes, where hfacac = hexafluoroacetylacetonate and M = FeII, NiII or CoII have been synthesized and characterized by chemical analysis, conductance measurements, i.r., electronic and e.p.r spectroscopies and by magnetic susceptibility measurements (in the 4.2–291K range). CoII and FeII are in a high spin state. [(VO)2Cl4(-bpym)] is paramagnetic, without significant interactions. [Fe2Cl4(-bpym)] shows a singular behaviour explained by an antiferromagnetic intradimer exchange and a ferromagnetic interdimer interaction. All other complexes are antiferromagnetic, with an intramolecular exchange parameter, J, varying from –3.3 cm–1 for CoII/math> to –109 cm–1 for CuII. 相似文献
13.
Thomas Reiner Alexander N. Marziale Florian J. Kiefer Jörg Eppinger 《Journal of organometallic chemistry》2010,695(24):2667-2672
Conversion of 4′-(2,5-dihydrophenyl)butanol or N-trifluoroacetyl-2,5-dihydrobenzylamine with MCl3·n H2O (M = Ru, Os) affords the corresponding dimeric η6-arene complexes in good to excellent yields. Under similar reaction conditions, the amine functionalized arene precursor 2,5-dihydrobenzylamine yields the corresponding Ru(II) complex. For osmium, HCl induced oxidation leads to formation of [OsCl6]2− salts. However, under optimized reaction conditions, conversion of the precursor 2,5-dihydrobenzylamine chloride results in clean formation of η6-arene Os(II) complex. X-ray structures of [(η6-benzyl ammonium)(dmso)RuCl2] and (2,5-dihydrobenzyl ammonium)4[OsCl6]2confirm the spectroscopic data. High stability towards air and acid as well as enhanced solubility in water is observed for all η6-arene complexes. 相似文献
14.
The ethylene/cyclopentadiene (CPD) copolymerization behavior by using fluoro-substituted bis(β-enaminoketonato) titanium complexes [FC6H4NC(CH3)CHCO(CF3)]2TiCl2 (1a–1c) has been investigated in detail. Upon utilizing MMAO as a cocatalyst, complexes 1a–1c exhibit high catalytic activities, affording the copolymers with high molecular weight and unimodal molecular weight distribution. Compared with non-substituted complex [C6H5NC(CH3)CHCO(CF3)]2TiCl2 (1), complexes 1a–1c can produce the copolymers with CPD incorporation adjusted in a wide range due to the enhancement of electrophilicity of metal center caused by introducing electron-withdrawing groups. Especially complex 1c bearing fluorine at the para-position of N-aryl moiety provides the highest CPD incorporation, which is nearly two times (18.5 mol%) higher than the non-substituted complex 1 (8.9 mol%) under the same conditions. The highest CPD incorporation up to 24.6 mol% can be easily achieved using this complex. 1H- and 13C-NMR spectra demonstrate that these fluoro-substituted complexes possess regioselective nature with exclusive 1,2-insertion fashion, and alternating ethylene-CPD sequence can be detected at high CPD incorporation. 相似文献
15.
Hai-Bao Duan Hong Zhou Zheng-Fang Tian Fang Xuan Xiao-Ming Ren 《Solid State Sciences》2009,11(7):1216-1221
The crystal structures and magnetic properties of two new ion-pair complexes, [N-NH2Py][Ni(mnt)2] (1) and [N-NH2Ql][Ni(mnt)2] (2) (N-NH2Py+ = 1-aminopyridinium, N-NH2Ql+ = 1-aminoquinolinium; mnt2? = maleonitriledithiolate) have been investigated. The differences of the molecular topology and size of the counter cation result in distinct anionic and cationic stacking patterns in the crystals, namely, in the crystal of 1 the anions (A) and cations (C) alternate to stack into a mixed column in the fashion of …AACCAACC…, and the neighboring columns are connected together via intermolecular H-bonding interactions as well as van der Waals forces; while, in the crystal of 2, the anions and cations alternate to form a mixed columnar stack in the manner of …ACAC…, and the adjacent columns are held together via weak van der Waals forces. Investigations of variable-temperature magnetic susceptibility indicated that 1 is a spin gap system but its magnetic behavior does not follow the Bleaney–Bowers spin dimer model; 2 shows a magnetic feature of linear decrease of χmT value upon cooling, and this kind of magnetic behavior is probably related to the presence of temperature independent paramagnetism. 相似文献
16.
Renée L. Beyer Hakan Kandemir Mohan Bhadbhade Ibrahim F. Sengul Chao-wei Leu Daniel Wenholz Naresh Kumar David StC. Black 《Tetrahedron letters》2018,59(51):4483-4486
Acylation reactions of 4,6-dimethoxyindoles with glyoxyloyl chlorides were achieved by the use of graphite powder in 1,2-dichloroethane at reflux. The products were monoketones as a result of decarbonylation, rather than the expected 1,2-diketones. Treatment of these monoketones with base led to their cyclisation and elimination of methanol to afford the novel dipyrrolo[2.3-a:1′,2′,3′-fg]acridin-12(1H)-ones. 相似文献
17.
《Journal of organometallic chemistry》2003,683(1):220-239
The alkylation of NiCl2py4 or PdCl2py2 with organomagnesium or organolithium reagents affords dialkyl complexes cis-MR2py2 (R=Me, CH2SiMe3, CH2Ph, CH2CMe2Ph, 2,4,6-C6H2Me3). The methyl and trimethylsilyl derivatives undergo ligand exchange reactions with chelating nitrogen ligands (α-diimines or 2-imidoylpyridines), yielding the corresponding dialkyl derivatives in good to excellent yields. A catalytic amount of PMe3 induces the transformation of the nickel complex Ni(CH2CMe2Ph)2py2 into the metallacyclic derivative .The latter, and the related palladacycle , also undergo facile ligand exchange reactions. 相似文献
18.
M.Z. Kassaee Z. Najafi F.A. Shakib M.R. Momeni 《Journal of organometallic chemistry》2011,696(10):2059-2064
The effects of alkyl, amino, phosphino, oxy, and thio moieties on the stability, multiplicity and reactivity of α-cyclopropylsilylenes with acyclic, cyclic, and unsaturated cyclic structures are compared and contrasted at B3LYP/AUG-cc-pVTZ//B3LYP/6-31G∗ level. The simultaneous stabilizing effects of heteroatom and cyclopropyl α-substituents on the above silylenes create the following trend of singlet-triplet energy gaps (?ES-T): amino ≈ oxy > thio > alkyl > phosphino. The ΔES-T values for all the above silylenes increase through cyclization, because cyclization stabilizes singlet states of all our α-heteroatom substitued silylenes while destabilizes their corresponding triplet states. The ΔES-T values for all the heteroatom substituted cyclic silylenes decrease upon unsaturation, due to the higher stabilization of triplet compared to the singlet state. Interestingly, isodesmic reactions showed the phosphino substituents stabilize the triplet more than the corresponding singlet states, not only in the unsaturated form but also in the acyclic and cyclic structures. This is in contrast to cyclopropyl which stabilizes singlet considerably more than the corresponding triplet states. The reactivity of the above silylenes is discussed in terms of nucleophilicity, and electrophilicity; showing phosphino- and aminocyclopropylsilylenes more nucleophilic than oxy- and thiocyclopropylsilylenes. 相似文献
19.
Dafa Chen 《Journal of organometallic chemistry》2006,691(18):3823-3833
Thermal treatment of C9H7SiMe2C9H7 and C9H7Me2SiOSiMe2C9H7 with Ru3(CO)12 in refluxing xylene gave the corresponding diruthenium complexes (E)[(η5-C9H6)Ru(CO)]2(μ-CO)2 [E = Me2Si (1), Me2SiOSiMe2 (2)]. A desilylation product [(η5-C9H7)Ru(CO)]2(μ-CO)2 (3) was also obtained in the latter case. Similar treatment of C9H7Me2SiSiMe2C9H7 with Ru3(CO)12 gave a novel indenyl nonanuclear ruthenium cluster Ru9(μ6-C)(CO)14(μ3-η5:η2:η2-C9H7)2 (5) with carbon-centered tricapped trigonal prism geometry, in addition to the diruthenium complex (Me2SiSiMe2)[(η5-C9H6)Ru(CO)]2(μ-CO)2 (4) and the desilylation product 3. Complex 4 can undergo a thermal rearrangement to form the product [(Me2Si)(η5-C9H6)Ru(CO)2]2 (6). The molecular structures of 1, 2, 4, 5, and 6 were determined by X-ray diffraction. 相似文献
20.
N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%). 相似文献