共查询到20条相似文献,搜索用时 31 毫秒
1.
Vasile Lozan 《Inorganica chimica acta》2009,362(3):793-11029
The dinuclear nickel(II) complex [Ni2L(Cl)]+ (1), where (L)2− represents a 24-membered binucleating hexamine-dithiophenolate ligand, reacts readily with primary and secondary amines RR′NH in the presence of CO2 (1 bar) to give dinuclear monoalkyl- and dialkylcarbamate complexes [Ni2L(O2CNRR′)]+ (R = H, R′ = CH2Ph (2), R = H, R′ = n-Bu (3), R = H, R′ = n-Oct (4), R = H, R′ = CH2CH2OH (5), R = R′ = Et (6), and R = R′ = CH2CH2OH (7)). Complexes 2-7 can also be prepared by the reaction of 1 with CO2(air)/amine. The carbamate complexes are hydrolyzed in methanolic solution to give the known alkylcarbonate complex [Ni2L(O2COMe)]+ (8). These conversions are less rapid than the transesterification reactions of 8, due to a less electron-demanding carboxyl C(carbamate) atom. All new complexes were either isolated as perchlorate or tetraphenylborate salts and fully characterized by elemental analysis, UV/Vis, and IR spectroscopy. The structures of 2[BPh4] and 7[BPh4] have also been determined by X-ray crystallography. They confirm the presence of μ1,3-bridging alkylcarbamate units in the products. 相似文献
2.
Kimberly Edwards Alexander R. Parent Kelley C. Shortsleeves Louise N. Dawe 《Inorganica chimica acta》2011,368(1):141-151
The reactions of metal(II) chlorides and bromides with 8-methylquinoline (8-mequin) in neutral and acidic solutions were investigated. The reaction with ZnCl2, ZnBr2, CoCl2, CoBr2, CuCl2 or CuBr2 with the appropriate HX in water or aqueous ethanol gave complexes of the formula (8-mequin)2MX4 (1, M = Cu, X = Cl; 2, M = Cu, X = Br; 3, M = Co, X = Cl; 4, M = Co, X = Br) or (8-mequin)2ZnX4·nH2O (5, X = Cl, n = 0; 6, X = Br, n = 0; 7, X = Cl, n = 1; 8, X = Br, n = 1). Crystals of 1, 2 and 4-8 suitable for single crystal X-ray diffraction were obtained and the structures reported. Compounds 1 and 2 crystallize in the monoclinic space group C2/c, while 4-8 crystallize in the triclinic space group, . Variable temperature magnetic susceptibility data indicate very weak interactions for the copper compounds 1 and 2, while the magnetic behavior of 3 and 4 is dominated by single ion anisotropy, with weaker antiferromagnetic interactions. 相似文献
3.
Euan K. Brechin Ulli Englert Guido Pampaloni Calogero Pinzino 《Inorganica chimica acta》2008,361(8):2375-2384
The synthesis and the characterization of several mono- and dinuclear middle transition metal derivatives of 1,10-phenanthroline-5,6-dione, 1, are presented. The reaction of 1 with CrCl2(THF)2 gives CrCl2(O,O′-C12H6N2O2)(THF)2, 2, while the halides of iron(II), cobalt(II) and nickel(II) afford adducts of general formula MX2(N,N′-C12H6N2O2), M = Fe, 4, Co, 5, X = Cl; M = Ni, 6, X = Br. DFT calculations on CrCl2(L)(THF)2 with L = O,O′-C12H6N2O2 or O,O′-C14H8O2 allowed a direct comparison of the coordination properties of 9,10-phenanthrenequinone and 1,10-phenanthroline-5,6-dione to be made. Dinuclear compounds of general formula CrCl2(THF)2(O,O′-C12H6N2O2-N,N′)MXnLm, M = Zr, 7, X = Cl, n = 4, m = 0; M = Cr, 8, X = Cl, n = 2, L = THF, m = 2; M = Fe, 9, Co, 10, X = Cl, n = 2, m = 0; M = Ni, 11, X = Br, n = 2, m = 0, are prepared from 2 and the corresponding metal halide, while VCp2(O,O′-C12H6N2O2-N,N′)FeCl2, 12, is synthesized by reacting 4 with VCp2. The electronic properties of the different complexes are investigated by magnetic moment measurements and EPR spectroscopy. 相似文献
4.
A series of osmium(VI) nitrido complexes containing pyridine-carboxylato ligands OsVI(N)(L)2X (L = pyridine-2carboxylate (1), 2-quinaldinate (2) and X = Cl (a), Br (1b and 2c) or CH3O (2b)) and [OsVI(N)(L)X3]− (L = pyridine-2,6-dicarboxylate (3) and X = Cl (a) or Br (b)) have been synthesised. Complexes 1 and 2 are electrophilic and react readily with various nucleophiles such as phosphine, sulfide and azide. Reaction of OsVI(N)(L)2X (1 and 2) with triphenylphosphine produces the osmium(IV) phosphiniminato complexes OsVI(NPPh3)(L)2X (4 and 5). The kinetics of nitrogen atom transfer from the complexes OsVI(N)(L)2Br (2c) (L = 2-quinaldinate) with triphenylphosphine have been studied in CH3CN at 25.0 °C by stopped-flow spectrophotometric method. The following rate law is obtained: −d[Os(VI)]/dt = k2[Os(VI)][PPh3]. OsVI(N)(L)2Cl (L = 2-quinaldinate) (2a) reacts also with [PPN](N3) to give an osmium(III) dichloro complex, trans-[PPN][OsIII(L)2Cl2] (6). Reaction of OsVI(N)(L)2Cl (L = 2-quinaldinate) (2a) with lithium sulfide produces an osmium(II) thionitrosyl complex OsII(NS)(L)2Cl (7). These complexes have been structurally characterised by X-ray crystallography. 相似文献
5.
Daniel Bandarra Telma Lopes Marta S. Saraiva Carla D. Nunes Paula Brandão Margarida Meireles Maria José Calhorda 《Journal of inorganic biochemistry》2010,104(11):1171-1177
Several molybdenum complexes, [Mo(η3-C3H5)X(CO)2(N-N)] (N-N = 1,10-phenanthroline, phen: X = CF3SO3T1, X = Br B1, X = Cl C1; N-N = 2,2′-bipyridyl, X = CF3SO3T2, X = Br B2) and [W(η3-C3H5)Br(CO)2(phen)] (W1) have been synthesized and characterized. Their antitumor properties have been tested in vitro against human cancer cell lines cervical carcinoma (HeLa) and breast carcinoma (MCF-7) using a metabolic activity test (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide, MTT), leading to IC50 values ranging from 3 to 45 μM, approximately. Most complexes exhibited significant antitumoral activity. Complexes B1 and T2 were chosen for subsequent studies aiming to understand their mechanism of action. Cellular uptake of molybdenum and octanol/water partition assays revealed that both B1 and T2 exhibit a selective uptake by cells and intermediate partition coefficients. The binding constants of B1 and T2 with ct DNA, as determined by absorption titration, are 2.08 (± 0.98) × 105 and 3.68 (± 2.01) × 105 M− 1, respectively. These results suggest that they interact with DNA changing its conformation and possibly inducing cell death, and may therefore provide a valuable tool in cancer chemotherapy. 相似文献
6.
Hong-Rong Zuo Qian Huang Jia-Rong Zhou Chun-Lin Ni Xue-Lei Hu 《Inorganica chimica acta》2009,362(10):3657-3662
Two new ion-pair complexes, [FBrBzPyN(CH3)2]2[Ni(mnt)2] (1) and [FBrBzPyN(CH3)2][Ni(mnt)2] (2) (mnt2− = maleonitriledithiolate, [FBrBzPyN(CH3)2]+ = [1-(4′-fluoro-2′-bromobenzyl)-4-dimethylaminopyridinium]) have been prepared and characterized by elemental analyses, UV, IR, single crystal X-ray diffraction and magnetic susceptibility. The cations (D) and the anions (A) in 1 stack into a 1D alternating column (i.e., of type ?DDADDADD?) via short S?Br, N?F, C?N interactions, and C-H?Br hydrogen bonds. The cation-cation π?π stacking interactions within the columns give further rise to a 2D network structure. Compound 2 forms a 3D structure in which the Ni(III) ions stack into a uniform 1D zigzag magnetic chain through Ni?S, Ni?Ni, or π?π interactions with a Ni?Ni distance of 4.024 Å. Magnetic susceptibility measurements in the temperature range 2-300 K show that 1 is expected to be diamagnetic, and 2 exhibits an interesting spin-gap transition (Δ/kb = 460.6 K) around 155 K. 相似文献
7.
The reactions of 1 equiv. of the ligand 3-(ethoxycarbonylmethyl-pyridin-2-ylmethyl-amino)-propionic acid methyl ester (2) with the Re(V) starting materials [ReOX3(PPh3)2] (X = Cl, Br) in refluxing chloroform yielded the Re(V)-oxo dihalide complexes [ReOX2{(C5H4NCH2)N(CH2CO2)(C2H4CO2CH3)}] (X = Cl, 3; X = Br, 4). The complexes were characterized by elemental analysis, NMR and IR spectroscopy, cyclic voltammetry and X-ray crystallography. Complex 3 displays distorted octahedral coordination geometry with the tridentate ligand coordinating facially to the Re(V) center. The carboxylate oxygen atom occupies an axial site trans to the ReO bond. The two chlorine atoms consequently adopt a cis configuration. 相似文献
8.
Complexes cis,trans-Fe(CO)2(PMe3)2RR′ (R = CH3, R′ = Ph (2); R = CH3, R′ = CHCH2 (3); R = CHCH2, R′ = Ph (4); R = R′ = CHCH2 (5); R = R′ = CH3 (6)) were prepared by reaction of cis,trans-Fe(CO)2(PMe3)2RCl (1) with organolithium reagents LiR′. All complexes were characterized in solution by IR and 1H, 31P and, in a few cases, 13C NMR mono- and bi-dimensional spectroscopies. Complexes 5 and 6 were structurally characterized by X-ray diffractometric methods. In solution complexes 2, 3 and 4 undergo slowly coupling of the σ-hydrocarbyl substituents leading to Fe(CO)3(PMe3)2 and other decomposition products. Complex 6 was very stable in solution in the absence of nucleophiles and in the solid state. Complex 5 transformed through intramolecular coupling of the vinyl groups into Fe(CO)(PMe3)2(η4-butadiene) (7), which was characterized in solution by IR and NMR spectroscopies. 相似文献
9.
Fabio Marchetti 《Inorganica chimica acta》2011,376(1):123-653
NbX5 (X = F, 1a; X = Cl, 1b) reacted with γ-butyrolactone (but), ε-caprolactam (cap), δ-valerolactam (val) in 1:1 M ratio in chlorinated solvent, affording either the neutral coordination adducts NbCl5L (L = but, 2a; L = val, 2b) or the ionic ones [NbX4L2][NbX6] (X = F, L = but, 3a; X = F, L = val, 3b; X = F, L = cap, 3c; X = Cl, L = cap, 3d). The reaction of 1a with equimolar amount of guanine (gua) in CH3CN resulted in the formation of the complex [NbF4(gua)2][NbF6], 3e. The addition of two equivalents of organic substrate to 1 gave selectively the compounds NbCl5L2 (L = but, 4a; L = val, 4b) or [NbF4L4][NbF6] (L = but, 5a; L = val, 5b; L = cap, 5c). The 1:2 M reaction of 1b with ε-caprolactam proceeded with C-N bond activation and afforded the derivative , 6, in high yield. 相似文献
10.
Michael C. Janzen 《Inorganica chimica acta》2005,358(5):1614-1622
The complex [PtMe2(bu2bpy)], 1, bu2bpy = 4,4′-di-t-butyl-2,2′-bipyridine reacts with mercury(II) halides HgX2 (X = Cl, Br, O2CCF3, O2CMe) to give the corresponding complexes [PtMe2X(HgX)(bu2bpy)], 2, by trans oxidative addition followed, when X = O2CCF3, O2CMe only, by easy isomerization to the cis isomers 3. The complexes 2 or 3 react with complex 1 to give the corresponding adducts [PtMe2X(bu2bpy)(μ-HgX)PtMe2X(bu2bpy)], 4, which are shown to contain both covalent and donor-acceptor Pt-Hg bonds in the solid state, and which exhibit very easy fluxionality in solution. 相似文献
11.
Xiang-Yong Lu 《Inorganica chimica acta》2009,362(14):5113-2011
Two tetra-nuclear Ag(I) complexes with styrene-functionalized N-heterocyclic carbene [AgL2]2[Ag2X4] (L = 1-methyl-3-(4-vinylbenzyl)imidazol-2-ylidene, X = Cl, 2a; X = I, 2b) were prepared by the reactions between the corresponding imidazolium salts with Ag2O. The reaction mixture was further treated with AgBF4 to give a mononuclear ion-pair complex [AgL2][BF4] (3). The molecular structures of these new Ag(I) complexes have been determined by X-ray diffraction analyses. 2a and 2b consist of two [Ag(L)2]+ fragments with the central [Ag2X4]2− anion held together by the close Ag(I)-Ag(I) interactions. Complex 3 is a mononuclear ion-pair complex with a linear bi-coordinate Ag fragment. 相似文献
12.
A family of four new phenoxo-bridged binuclear manganese(III) complexes of the general formula, [Mn(L)(X)]2 where L = [N,N′-bis(salicylidene)]propane-1,2-diamine and X = salicylaldehyde anion (sal−) (1); NCS− (2); NCO− (3) and [Mn(L′)(N3)]2·2C2H5OH (4) where L′ = [N,N′-bis(2-hydroxyacetophenylidene)]propane-1,2-diamine has been prepared. The syntheses have been achieved by reacting manganese perchlorate with 1,2-diaminopropane and salicylaldehyde (or 2-hydroxyacetophenone for 4) or along with the respective pseudohalides so that the tetradentate Schiff base H2L or H2L′ is obtained in situ to bind the Mn(III) ion. The complexes have been characterized by IR spectroscopy, elemental analysis, crystal structure analysis and variable-temperature magnetic susceptibility measurements. The single crystal X-ray diffraction studies show that the compounds are isostructural containing dimeric Mn(III) units with bridging phenolate oxygen atoms. Low temperature magnetic studies indicate that the complexes 1-3 exhibit intradimer ferromagnetic exchange as well as single-molecule magnet (SMM) behavior while complex 4 is found to undergo an intradimer antiferromagnetic coupling. 相似文献
13.
The dinuclear bis(6-X-pyridin-2-olato) ruthenium complexes [Ru2(μ-XpyO)2(CO)4(PPh3)2] (X = Cl (4B) and Br (5B)), [Ru2(μ-XpyO)2(CO)4(CH3CN)2] (X = Cl (6B), Br (7B) and F (8B)) and [Ru2(μ-ClpyO)2(CO)4(PhCN)2] (9B) were prepared from the corresponding tetranuclear coordination dimers [Ru2(μ-XpyO)2(CO)4]2 (1: X = Cl; 2: X = Br) and [Ru2(μ-FpyO)2(CO)6]2 (3) by treatment with an excess of triphenylphosphane, acetonitrile and benzonitrile, respectively. In the solid state, complexes 4B-9B all have a head-to-tail arrangement of the two pyridonate ligands, as evidenced by X-ray crystal structure analyses of 4B, 6B and 9B, in contrast to the head-to-head arrangement in the precursors 1-3. A temperature- and solvent-dependent equilibrium between the yellow head-to-tail complexes and the red head-to-head complexes 4A-7A and 9A, bearing an axial ligand only at the O,O-substituted ruthenium atom, exists in solution and was studied by NMR spectroscopy. Full 1H and 13C NMR assignments were made in each case. Treatment of 1 and 2 with the N-heterocyclic carbene (NHC) 1-butyl-3-methylimidazolin-2-ylidene provided the complexes [Ru2(μ-XpyO)2(CO)4(NHC)], X = Cl (11A) or Br (12A). An XRD analysis revealed the head-to-head arrangement of the pyridonate ligands and axial coordination of the carbene ligand at the O,O-substituted ruthenium atom. The conversion of 11A and 12A into the corresponding head-to-tail complexes was not possible. 相似文献
14.
The nuclearity, bonding and H-bonded networks of copper(I) halide complexes with thiophene-2-carbaldehyde thiosemicarbazones {(C4H3S)HC2N3-N(H)-C1(S)N1HR} are influenced by R substituents at N1 atom. Thiophene-2-carbaldehyde-N1-methyl thiosemicarbazone (HttscMe) or thiophene-2-carbaldehyde-N1-ethyl thiosemicarbazone (HttscEt) have yielded halogen-bridged dinuclear complexes, [Cu2(μ-X)2(η1-S-Htsc)2(Ph3P)2] (Htsc, X: HttscMe, I, 1; Br, 2; Cl, 3; HttscEt, I, 4; Br, 5; Cl, 6), while thiophene-2-carbaldehyde-N1-phenyl thiosemicarbazone (HttscPh) has yielded mononuclear complexes, [CuX(η1-S-HttscPh)2] (X, I, 7a; Br 8; Cl, 9) and a sulfur bridged dinuclear complex, [Cu2(μ-S-HttscPh)2(η1-S-HttscPh)2I2] 7b co-existing with 7a in the same unit cell. These results are in contrast to S-bridged dimers [Cu2(μ-S-Httsc)2(η1-Br)2(Ph3P)2] · 2H2O and [Cu2(μ-S-Httsc)2(η1-Cl)2(Ph3P)2] · 2CH3CN obtained for R = H and X = Cl, Br (Httsc = thiophene-2-carbaldehyde thiosemicarbazone) as reported earlier. The intermolecular CHPh?π interaction in 1-3 (2.797 Å, 1; 3.264 Å, 2; 3.257 Å, 3) have formed linear polymers, whereas the CHPh?X and N3?HCH interactions in 4-6 (2.791, 2.69 Å, 5; 2.776, 2.745 Å, 6, respectively) have led to the formation of H-bonded 2D polymer. The PhN1H?π, interactions (2.547 Å, 8, 2.599 Å, 9) have formed H-bonded dimers only. The Cu?Cu separations are 3.221-3.404 Å (1-6). 相似文献
15.
Beno?ˆt Le Gall Nathalie Cosquer Jean Sala-Pala Estelle Vigier Philippe Molinié 《Inorganica chimica acta》2005,358(8):2513-2522
The reactions between the copper (II) salts [CuXL]PF6 (L: 2,6-[1-(2,6-diisopropylphenylimino)ethyl]pyridine) (X = Cl 1, X = Br 2) and LiTCNQ, in a DMF/water mixture, or Et3NH(TCNQ)2, in acetone, produced the new complexes [CuXL(TCNQ)] (X = Cl 3, X = Br 4). For both compounds, crystallographic studies have clearly evidenced the existence of dimeric complexes [{CuClL}(TCNQ)]2 owing to π-π overlap between two adjacent TCNQ− radical anions. Compound 1 reacted with Et4N(C10N7) to afford the mononuclear derivative [CuClL(C10N7)] (5), while its reaction with K2C10N6 produced the dinuclear complex [(CuClL)2(C10N6)] (6). The crystal structures of complexes 5 and 6 have been determined by X-ray crystallography. Magnetic studies have revealed that compound 6 displays weak antiferromagnetic interactions between the two metal centres, conversely compounds 3 and 5 exhibit purely paramagnetic behaviours. 相似文献
16.
Hong-Yan Li Jing Xiong Qiu-Lei Xu Yun-Mei Tao Jing-Lin Zuo 《Inorganica chimica acta》2011,370(1):398-3327
Six complexes (1-6) with the type of [Ru(bpy)2L]X2 (1-3: L = L1-L3, X = Cl−; 4-6: L = L1-L3, X = PF6−) were synthesized based on 2,2′-bipyridine and three 2,2′-bipyridine derivatives L1, L2 and L3 (L1 = 5,5′-dibromo-2,2′-bipyridine, L2 = 5-bromo-5′-carbazolyl-2,2′-bipyridine, L3 = 5,5′-dicarbazolyl-2,2′-bipyridine). The complexes 1-6 were characterized by 1H NMR, MS(ESI) and IR spectra, along with the X-ray crystal structure analysis for 1, 5 and 6. Their photophysical properties and electrochemiluminescence (ECL) properties were investigated in detail. In the UV-Vis absorption spectra, all complexes 1-6 show strong intraligand (π → π∗) transitions and metal-ligand charge transfer (MLCT, dπ (Ru) → π∗) bands. Upon the excitation wavelengths at ∼508 nm, all complexes 1-6 exhibit typical MLCT emission of ruthenium(II) polypyridyl complexes. The introduction of carbazole moieties improves the MLCT absorption and emission intensity. The ruthenium(II) complexes 1-6 exhibit good electrochemiluminescence (ECL) properties in [Ru(bpy)2L]2+/tri-n-propylamine (TPrA) acetonitrile solution and the complexes with PF6− showed higher ECL emission intensity than that of the complexes with Cl− based on the same ligands. 相似文献
17.
Damir A. Safin Maria G. Babashkina Dmitriy B. Krivolapov Airat R. Bashirov 《Inorganica chimica acta》2011,366(1):19-26
The reaction of [ZnLI,II2] (LI = [NH2C(S)NP(O)(OiPr)2]−; LII = [PhNHC(S)NP(O)(OiPr)2]−) or [Cd2LIV4] (LIV = [PhC(S)NP(O)(OiPr)2]−) with 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) leads to the heteroligand complexes [Zn(bpy)LI,II2], [Zn(phen)LI,II2], [Cd(bpy)LIV2] or [Cd(phen)LIV2], respectively. The introduction of the diimine ligands into the coordination sphere of the metal cation provokes a change from 1,5-O,S- to 1,3-N,S-coordination of the anionic ligands for Zn but not for the Cd species. The reaction of [Zn(phen)LIV2] (LIV = PhC(S)NP(O)(OiPr)2−) with CH2Cl2 cleaves the chlorine atoms from CH2Cl2 and leads to the formation of [Zn(phen)LIVCl] and S,S′-bis(benzimidothio-N-diisopropoxyphosphoryl)methane (LIV-CH2-LIV) in high yields. Using CHCl3 or CCl4 instead of CH2Cl2 does not lead to the formation of chlorine substituted products even under reflux conditions. The new compounds were investigated by 1H and 31P{1H} NMR, IR spectroscopy and microanalysis. Crystal structures of [ZnLII2], [Cd(phen)LIV2]·CH2Cl2, [Zn(bpy)LI2] and [Zn(phen)LIVCl] were elucidated by X-ray diffraction. 相似文献
18.
Luigi Busetto Fabio Marchetti Stefano Zacchini Valerio Zanotti 《Inorganica chimica acta》2005,358(5):1469-1484
The new diiron alkynyl methoxy carbene complexes [Fe2{μ-CN(Me)(R)}(μ-CO)(CO){C(OMe)CCR′}(Cp)2]+ (R = 2,6-Me2C6H3 (Xyl), R′ = Tol, 3a; R = Xyl, R′ = Ph, 3b; R = Xyl, R′=Bun, 3c; R = Xyl, R′=SiMe3, 3d; R = Me, R′ = Tol, 3e; R = Me, R′ = Ph, 3f) are obtained in two steps by addition of R′CCLi (R′ = Tol, Ph, Bun, SiMe3) to the carbonyl aminocarbyne complexes [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)2(Cp)2]+ (R = Xyl, 1a; Me, 1b), followed by methylation of the resulting alkynyl acyl compounds [Fe2{μ-CN(Me)(R)}(μ-CO)(CO){C(O)CCR′}(Cp)2] (R = Xyl, R′ = Tol, 2a; R = Xyl, R′ = Ph, 2b; R = Xyl, R′ = Bun, 2c; R = Xyl, R′ = SiMe3, 2d; R = Me, R′ = Tol, 2e; R = Me, R′ = Ph, 2f). Complexes 3 react with secondary amines (i.e., Me2NH, C5H10NH) to give the 4-amino-1-metalla-1,3-dienes [Fe2{μ-CN(Me)(R)}(μ-CO)(CO){C(OMe)CHC(R′)(NMe2)}(Cp)2]+ (R = Xyl, R′ = Tol, 4a; R = Xyl, R′ = Ph, 4b; R = Me, R′ = Ph, 4c) and [Fe2{μ-CN(Me)(Xyl)}(μ-CO)(CO){C(OMe)CHC(Tol)(NC5H10)}(Cp)2]+, 5. The addition occurs stereo-selectively affording only the E-configured products. Analogously, addition of primary amines R′NH2 (R′ = Ph, Et, Pri) affords the 4-(NH-amino)-1-metalla-1,3-diene complexes [Fe2{μ-CN(Me)(Xyl)}(μ-CO)(CO){C(OMe)CHC(R)(NHR′)}(Cp)2]+ (R = Ph, 6a; Et, 6b; Pri, 6c). In the case of 6a, only the E isomer is formed, whereas a mixture of the E and Z isomers is present in the case of 6b,c, with prevalence of the latter. Moreover, the two isomeric forms exist under dynamic equilibrium conditions, as shown by VT NMR studies. Complexes 6 are deprotonated by strong bases (e.g., NaH) resulting in the formation of the neutral vinyl imine complexes [Fe2{μ-CN(Me)(Xyl)}(μ-CO)(CO){C(OMe)CHC(NR)(Tol)}(Cp)2] (R = Ph, 7a; Et, 7b; Pri, 7c); the reaction can be reverted by addition of strong acids. X-ray crystal structures have been determined for 3a[CF3SO3] · Et2O, 4c[CF3SO3], 6a[BF4] · CH2Cl2, 6c[CF3SO3] · 0.5Et2O and 7a · CH2Cl2. 相似文献
19.
Naokazu Yoshikawa Shinichi Yamabe Yasushi Kai Keiichi Tsukahara 《Inorganica chimica acta》2006,359(14):4585-4593
A series of mononuclear acetonitrile complexes of the type [Ru(CH3CN)(L)(terpy)]2+ {L = phen (1), dpbpy (3), and bpm (5)}, and their reference complexes [RuCl(L)(terpy)]+ {L = phen (2), dpbpy (4), and dpphen (6)} were prepared and characterized by electrospray ionization mass spectrometry, UV-vis spectroscopy, and cyclic voltammograms (CV). Abbreviations of the ligands (Ls) are phen = 1,10-phenanthroline, dpbpy = 4,4′-diphenyl-2,2′-bipyridine, bpm = 2,2′-bipyrimidine, dpphen = 4,7-diphenyl-1,10-phenanthroline, bpy = 2,2′-bipyridine, and terpy = 2,2′:6′,2″-terpyridine. The X-ray structures of the two complexes 2 and 3 were newly obtained. The metal-to-ligand charge transfer (MLCT) bands in the visible region for 1, 3, and 5 in acetonitrile were blue shifted relative to those of the reference complexes [RuCl(L)(terpy)]+. CV for all the [Ru(CH3CN)(L)(terpy)]2+ complexes showed the first oxidation wave at around 0.95 V, being more positive than those of [RuCl(L)(terpy)]+. The time-dependent-density-functional-theory approach (TDDFT) was used to interpret the absorption spectra of 1 and 2. Good agreement between computed and experimental absorption spectra was obtained. The DFT approach also revealed the orbital interactions between Ru(phen)(terpy) and CH3CN or Cl−. It is demonstrated that the HOMO-LUMO energy gap of the acetonitrile ligand is larger than that of the Cl− one. 相似文献
20.
A series of chiral Ag(I) and Cu(II) complexes have been prepared from the reaction between AgX (X = NO3, PF6, OTf) or CuX2 (X = Cl, ClO4) and chiral biaryl-based N-ligands. The rigidity of the ligand plays an important role in the Ag(I) complex formation. For example, treatment of chiral N3-ligands 1-3 with half equiv of AgX (X = NO3, PF6, OTf) gives the chiral bis-ligated four-coordinated Ag(I) complexes, while ligand 4 affords the two-coordinated Ag(I) complexes. Reaction of AgX with 1 equiv of chiral N4-ligands 5, 7, 8 and 10 gives the chiral, binuclear double helicate Ag(I) complexes, while chiral mono-nuclear single helicate Ag(I) complexes are obtained with N4-ligands 6 and 9. Treatment of either N3-ligand 1 or N4-ligand 9 or 10 with 1 equiv of CuX2 (X = Cl, ClO4) gives the mono-ligated Cu(II) complexes. All the complexes have been characterized by various spectroscopic techniques, and elemental analyses. Seventeen of them have further been confirmed by X-ray diffraction analyses. The Cu(II) complexes do not show catalytic activity for allylation reaction, in contrast to Ag(I) complexes, but they do exhibit catalytic activity for Henry reaction (nitroaldol reaction) that Ag(I) complexes do not. 相似文献