首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 78 毫秒
1.
A series of new indanimine ligands [ArN?CC2H3(CH3)C6H2(R)OH] (Ar = Ph, R = Me ( 1 ), R = H ( 2 ), and R = Cl ( 3 ); Ar = 2,6‐i‐Pr2C6H3, R = Me ( 4 ), R = H ( 5 ), and R = Cl ( 6 )) were synthesized and characterized. Reaction of indanimines with Ni(OAc)2·4H2O results in the formation of the trinuclear hexa(indaniminato)tri (nickel(II)) complexes Ni3[ArN = CC2H3(CH3)C6H2(R)O]6 (Ar = Ph, R = Me ( 7 ), R = H ( 8 ), and R = Cl ( 9 )) and the mononuclear bis(indaniminato)nickel (II) complexes Ni[ArN?CC2H3(CH3)C6H2(R)O]2 (Ar = 2,6‐i‐Pr2C6H3, R = Me ( 10 ), R = H ( 11 ), and R = Cl ( 12 )). All nickel complexes were characterized by their IR, NMR spectra, and elemental analyses. In addition, X‐ray structure analyses were performed for complexes 7 , 10 , 11 , and 12 . After being activated with methylaluminoxane (MAO), these nickel(II) complexes can polymerize norbornene to produce addition‐type polynorbornene (PNB) with high molecular weight Mv (106 g mol?1), highly catalytic activities up to 2.18 × 107 gPNB mol?1 Ni h?1. Catalytic activities and the molecular weight of PNB have been investigated for various reaction conditions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 489–500, 2008  相似文献   

2.
Tris(triphenylphosphane)nickel(0) Complexes with Nitrile Ligands . Synthesis, properties and reaction behaviour of (Ph3P)3Ni(η1-NCR) (R = PhCH2, 2-MeC6H4, Me3Si) complexes as well as the X-ray structure of (Ph3P)3Ni(η1-NCSiMe3) are described. With NC(CH2)nBr (n = 1, 2) instead of the analogous nitrile complexes (Ph3P)2NiBr2 and CH3CN or C2H5CN respectively are formed.  相似文献   

3.
Investigation on the Alkylation of Bis-Stilbendithiolato Complexes of NiII, PdII, and PtII Alkylation reactions of co-ordinated ligands of the type of ethylene-bisthiol R2S2C22-proceed different depending on the substituents R. The neutral complexes isolated by a alkylation of the nickel bis-chelates (R = phenyl) according to Schrauzer and Rabinowitz and formulated by these authors as mixed ligand chelates of dithiolate and diether, were identified by us as complexes of the monoethers of the ligand. These nickel (II) complexes of the mono-ethers can not be alkylated further by alkyliodides. Oxidative coupling of two ligands yields disulfides which have been identified by mass spectroscopy thus indicating the original position of attack of the alkylating reagent. The formation of bis-monether complexes is reflected by the different charges on the S atoms of the model complex [Ni(CH3S2C2H2)(S2C2H2)]- obtained from EHT and CNDO calculations. Both possible stereo-isomers have been isolated of the bis-methylmonether complex of Pt(II). Trans-[M((CH3)(S2C2Ph2))2] (M = Ni(II), Pd(II)) form CH2Cl2 adducts. By treating the Ni-bis complexes of the monoalkylthioethers with iodine polyiodides are prepared. Binuclear Pd(II) complexes of composition [Pd2((R)(S2C2Ph2))2Cl2] could be prepared by metal exchange.  相似文献   

4.
Aluminiumorganic compounds of a coordinated salicylaldoxime resulted from reaction of M(II)(SALOxH)2 (where M(II) = Ni(II), Pd(II) and Cu(II); SALOx represents the divalent radical of the salicylaldoxime) with AlR3(R = CH3,C2H5,i‐C4H9,C6H5 and Cl). Copper(II) bis‐salicylaldoximate reacting with Al(i‐C4H9)3 does not form a compound similar to those obtained with nickel and palladium. Aluminiumorganic compounds of the coordinated salicylaldoxime result from the substitution of O? H?O hydrogen bonds, existing in chelates, by O? Al? O bridges. All compounds reported in this paper were separated from the reaction mixture as coloured powders and were characterized by chemical analyses, IR spectroscopy, X‐ray diffraction spectra, proton NMR spectra and magnetic properties. The new aluminiumorganic compounds form adducts with amine. Among the amine adducts, only the adducts with pyridine were isolated to confirm their formula and the mode of binding. Copyright © 2001 John Wiley & Sons, Ltd.  相似文献   

5.
1,2-Bis-(triphenylphosphorane-ylidene-amino)ethane as a Bidentate Ligand in Transition Metal Complexes The reactions of Ph3P?N? C2H4? N?PPh3 with transition metal halogenides MX2 give according to eq. (1) novel bisiminophosphorane complexes of the type M(Ph3PNC2H4 NPPh3)X2 (M ? Co, X ? Cl 1 a , Br 1 b , J 1 c ; M ? Ni, X ? Cl 2 a , Br 2 b , J 2 c , M ? Hg, X ? Cl 3 , M ? Cd, X ? Cl 4 ). The preparation, properties, magnetic moments, and structure of the new complexes are reported  相似文献   

6.
Dimeric chlorobridge complex [Rh(CO)2Cl]2 reacts with two equivalents of a series of unsymmetrical phosphine–phosphine monoselenide ligands, Ph2P(CH2)nP(Se)Ph2 {n = 1( a ), 2( b ), 3( c ), 4( d )}to form chelate complex [Rh(CO)Cl(P∩Se)] ( 1a ) {P∩Se = η2‐(P,Se) coordinated} and non‐chelate complexes [Rh(CO)2Cl(P~Se)] ( 1b–d ) {P~Se = η1‐(P) coordinated}. The complexes 1 undergo oxidative addition reactions with different electrophiles such as CH3I, C2H5I, C6H5CH2Cl and I2 to produce Rh(III) complexes of the type [Rh(COR)ClX(P∩Se)] {where R = ? C2H5 ( 2a ), X = I; R = ? CH2C6H5 ( 3a ), X = Cl}, [Rh(CO)ClI2(P∩Se)] ( 4a ), [Rh(CO)(COCH3)ClI(P~Se)] ( 5b–d ), [Rh(CO)(COH5)ClI‐(P~Se)] ( 6b–d ), [Rh(CO)(COCH2C6H5)Cl2(P~Se)] ( 7b–d ) and [Rh(CO)ClI2(P~Se)] ( 8b–d ). The kinetic study of the oxidative addition (OA) reactions of the complexes 1 with CH3I and C2H5I reveals a single stage kinetics. The rate of OA of the complexes varies with the length of the ligand backbone and follows the order 1a > 1b > 1c > 1d . The CH3I reacts with the different complexes at a rate 10–100 times faster than the C2H5I. The catalytic activity of complexes 1b–d for carbonylation of methanol is evaluated and a higher turnover number (TON) is obtained compared with that of the well‐known commercial species [Rh(CO)2I2]?. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

7.
Reaction of alkali metal halides (MX) with methylenediphosphine oxides and various related compounds in nonaqueous solutions leads to the formation of complex compounds. The compositions, properties, and stabilities of these compounds, which have been studied in detail in acetonitrile, are determined by the nature of the cations and anions of the alkali metal halides. Formation of neutral complexes with the composition [MX · L] and cationic complexes with the composition [ML]+ has been established. The most characteristic representative of complexes of the first type is [NaI · L]; in the complexes studied, L=R2P(O)CH2P(O)R2 (R=Bu, BuO, or Ph), Ph2P(O)CH2P(O) (OC2H5)CH2P(O)Ph2 and (p-OCH3C6H4)2P(O)CH2P(O)(C6H4CF3-p)2. Compound [LiL]+ is characteristic of complexes of the second type; the compounds containing Ph3P(O), Ph2P(O)CH2P(O)Ph2, and Ph2P(O)CH2P(O)(OC2H5)CH2P(O)Ph2 as ligands have been studied. Stability constants of the complexes [NaI · L] and [LiL]+ have been determined by measuring the dependence of the electrical conductivity of solutions of the alkali metal halides in acetonitrile on the concentration of the ligands. The complex-forming power of phosphine oxides increases with increase in the number of P=O groups. Stabilities of the complexes [NaI · L] with ligands with identical structure decrease with increase in the electronegativity of the substituents on the phosphorus atoms.  相似文献   

8.
The meta‐terphenyl diphosphine, m‐P2, 1 , was utilized to support Ni centers in the oxidation states 0, I, and II. A series of complexes bearing different substituents or ligands at Ni was prepared to investigate the dependence of metal–arene interactions on oxidation state and substitution at the metal center. Complex (m‐P2)Ni ( 2 ) shows strong Ni0–arene interactions involving the central arene ring of the terphenyl ligand both in solution and the solid state. These interactions are significantly less pronounced in Ni0 complexes bearing L‐type ligands ( 2‐L : L=CH3CN, CO, Ph2CN2), NiIX complexes ( 3‐X : X=Cl, BF4, N3, N3B(C6F5)3), and [(m‐P2)NiIICl2] ( 4 ). Complex 2 reacts with substrates, such as diphenyldiazoalkane, sulfur ylides (Ph2S?CH2), organoazides (RN3: R=para‐C6H4OMe, para‐C6H4CF3, 1‐adamantyl), and N2O with the locus of observed reactivity dependent on the nature of the substrate. These reactions led to isolation of an η1‐diphenyldiazoalkane adduct ( 2‐Ph2CN2 ), methylidene insertion into a Ni? P bond followed by rearrangement of a nickel‐bound phosphorus ylide ( 5 ) to a benzylphosphine ( 6) , Staudinger oxidation of the phosphine arms, and metal‐mediated nitrene insertion into an arene C? H bond of 1 , all derived from the same compound ( 2 ). Hydrogen‐atom abstraction from a NiI–amide ( 9 ) and the resulting nitrene transfer supports the viability of Ni–imide intermediates in the reaction of 1 with 1‐azido‐arenes.  相似文献   

9.
Treatment of complexes of the type [M(CO)4{(Ph2P)2CCH2}] (M = W, Mo or Cr) with functionalized lithium reagents, LiR, followed by hydrolysis gives complexes of the type [M(CO)4{PH2P)2CHCH2R}] in high yields; R = C6H4Me-4, C6H4OMe-2, C6H3(OMe)2-2,6, C6H4OH-2, C6H4(COOH)-2, CH2COPh or CH2COMe. IR, and 31P and 1H NMR data are given.  相似文献   

10.
Oxidation of Nickel(0) Complexes by Cyclic Imides of Dicarbonic Acids Normally, phthalimide (PI? H) or succinimide (SI? H) react with nickel(0) complexes — (dipy)Ni(COD) or (Ph3P)2Ni(C2H4) — by oxidative addition. The reaction of PI? H and the strong reductant (dipy)Ni(COD) is initiated by a one-electron transfer. Depending on the solvent, the resulting ion pair affords (dipy)NiI(PI) by spontaneous fragmentation or (dipy)NiII(H)(PI) by cage collaps. No interaction is found between the weak reductant (Ph3P)Ni(C2H4) and PI? H. Phosphine-containing nickel(0) complexes are electrophilically attacked by the acid NH group of SI? H. Hydrido complexes of nickel(0), such as (Cy3P)2Ni(H)(SI), or secondary products of them, such as [(SI)Ni(THF)]2NH, are formed. On the other hand, the reaction with (dipy)Ni(COD) affords only the binuclear substitution product [(dipy)Ni]2(SI? H)(THF). In solution prolongated heating of (dipy)Ni(PI)(THF)0,5 results in a partial decarbonylation. In contrast to the reaction of (dipy)Ni(COD) and cyclic carbonic acid anhydrides, no definite metalla rings but by an interaction with the solvent, benzamide is formed. With (dipy)Ni(COD) maleinimide does not react like on NH-acidic compound but like a polar olefine by substitution.  相似文献   

11.
Three new (N‐diphenylphosphino)‐isopropylanilines, having isopropyl substituent at the carbon 2‐ (1) 4‐ (2) or 2,6‐ (3) were prepared from the aminolysis of chlorodiphenylphosphine with 2‐isopropylaniline, 4‐isopropylaniline or 2,6‐diisopropylaniline, respectively, under anaerobic conditions. Oxidation of 1,2 and 3 with aqueous hydrogen peroxide, elemental sulfur or gray selenium gave the corresponding oxides, sulfides and selenides (Ph2P?E)NH? C6H4? 2‐CH(CH3)2, (Ph2P?E)NH? C6H4? 4‐CH(CH3)2 and (Ph2P?E)NH? C6H4? 2,6‐{CH(CH3)2}2, where E = O, S, or Se, respectively. The reaction of [M(cod)Cl2] (M = Pd, Pt; cod = 1,5‐cyclooctadiene) with two equivalents of 1,2 or 3 yields the corresponding monodendate complexes [M((Ph2P)NH? C6H4? 2‐CH(CH3)2)2Cl2], M = Pd 1d, M = Pt 1e, [M((Ph2P)NH? C6H4? 4‐CH(CH3)2)2Cl2], M = Pd 2d, M = Pt 2e and [M((Ph2P)NH? C6H4? 2,6‐(CH(CH3)2)2)2Cl2], M = Pd 3d, M = Pt 3e, respectively. All the compounds were isolated as analytically pure substances and characterized by NMR, IR spectroscopy and elemental analysis. Furthermore, representative solid‐state structure of [(Ph2P?S)NH? C6H4? 4‐CH(CH3)2] (2b) was determined using single crystal X‐ray diffraction technique. The complexes 1d–3d were tested and found to be highly active catalysts in the Suzuki coupling and Heck reaction, affording biphenyls and stilbenes, respectively. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

12.
Chemistry of Polyfunctional Molecules. 82. New Rhodium(1) Chelate Complexes with N,N-Bis(diphenylphosphino) alkyl- and -arylamines . [Rh(μ-Cl)(CO)2]2 ( 1 ) reacts with (Ph2P)2NR (2, a: R = C6H5, b: R = p-C6H4CH3) in a molar ratio of 1:2 to give the square plane, ionic complexes [Rh{(PH2P)2NR}2] [cis-Rh(CO)2Cl2] ( 3a, b ). By the reactions of [Rh(μ-Cl)(C8H12)]2(C8H12 = 1.5-Cyclooctadiene) (4) with (Ph2P)2NR ( 2a–d ) (c: R = CH3, d: R = C2H5) in the molar ratios of 1:4 the square plane 1:1 electrolytes [Rh{(Ph2P)2NR}2]Cl ( 5a–d ) are obtained. Upon treatment of 5a–d in dichloromethane with CO the complexes [Rh(CO){(Ph2P)2NR}2]Cl ( 6a–d ) are formed. They are only stable in solution and in CO atmosphere and were identified by infrared spectroscopy. The new complexes have been characterized, as far as possible, by conductometry, IR; FIR, Raman, 31P-NMR, and 1H-NMR spectra.  相似文献   

13.
Polarographic reduction half-wave potentials for the series of inorganic complexes M(RC5H4N)2Cl2 (M=Co(II), Ni(II), Cu(II), Zn(II), Cd(II); R=H, CH3, NH2, OH, CONH3, CHO, COCH2 COPh, Cl, Br and CH2OH) are reported to show the substituent effects in these complexes. Consequently, the E1/2 values correlated linearly with Hammett substituent parameters, the slope of the Eσ Vs σ plots evidently decreases in order of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II).  相似文献   

14.
Oxidation of Nickel(0) Complexes by Halogen Compounds of Cobalt(II), Copper(II), and Zine(II) In aceton as a solvent Ni(PPh3)4 is oxidized by; cobalt(II) complexes of the type (Ph3P)2CoX2 to nickel(I) compounds. In the case of X = Cl (Ph3P)3NiCl and (Ph3P)3CoCl separately crystallize, while for X = Br the lattice compound CoNi(PPh3)6Br2 and for X = I CoNi(PPh3)5I2 are formed. CuBr2 and Ni(PPh3)4 react to (Ph3P)2NiBr and (Ph3P)nCuBr. With (Ph3P)2ZnCl2 also (Ph3P)3NiCl is formed But in this case the oxidant is hydrogen chloride originating from hydrolysis. The magnetic moments of the new compounds were measured and their vis and fir spectra compared with those of the simple compounds (Ph3P)nNiX (n = 2, 3) and (Ph3P)3CoX. The M–X stretching frequencies are assigned. The cobalt (I) complexes (Ph3P)3CoCl have identical (distorted tetrahedral) structures, but most probably the nickel (I) complexes have not.  相似文献   

15.
The 5,5′-thiodisalicylato complexes of nickel(II) with water, ammonia, methylamine and pyridine were synthesized and their structure established to be [Ni(TDSA)L2·nH2O], where TDSA = 5,5′-thiodisalicylic acid, [C6H3(OH)(COOH)SC6H3(OH)(COOH)]. LH2O, NH3 CH3NH2 or pyridine, and n=3 for H2O, 2 for NH3 and CH3NH3, and 1 for pyridine complexes, from elemental analysis, IR and electronic spectroscopy, and magnetic susceptibility measurement. The thermal behaviour of the complexes has been studied by TG and DTA. TG shows three main steps of decomposition, viz. dehydration, axial base liberation, and decarboxylation leading to the formation of NiO at the final stage.  相似文献   

16.
The ligand 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene ( 1 ) has been used to prepare complexes of the type [PtL( 1 )] (L ? C2H4, CH2?CH? CO2Me, PhC?CPh, MeC?CMe, MeO2CC?CCO2Me, (i-Pr)O2CC?CCO2(i-Pr), Ph3P and CO). It is shown that these complexes are less labile than the corresponding species [PtL(Ph3P)2]. The preparation of complexes trans-[PtX(R)(1)] by oxidative addition of RX (RX ? PhCH2Br and Mel) to [Pt(C2H4)(1)] is described. The isolation of [PtO2(CH3)2CO(1)] is also reported.  相似文献   

17.
The effect of substituent at the sulfonyl group on the physicochemical properties and complexing ability of the sulfonyl derivatives of 2-ethylhexanoic acid hydrazide of the general formula C4H9CH(C2H5)C(O)·NHNHSO2C6H5R [R = H, CH3, NO2, NHC(O)CH3, Cl] with respect to Cu(II), Co(II), and Ni(II) ions was studied.  相似文献   

18.
The rates of the thermal reaction of the nickel(0) complex Ni[P(C2H5)3]4 with the alkyl halides CH3Br, CH3I in toluene have been compared with those of the reactions of the nickel(I) complexes Ni(X)[P(C2H5)3]3 (X  Br,I). The organic products from CH3X are methane and ethane, and those from C2H5I are ethane and ethylene. The reactivity of the nickel(I) complexes is 10–20 times less than that of the nickel(0) complex. The result suggest that the first step of the reaction of nickel(0) with CH3I is the expected oxidative addition of the halide to the metal substrate. The intermediate thus formed decomposes to produce ethane (and small amounts of methane) without further reaction with the organic halide. This mechanism is supported by deuterium-labeling experiments.  相似文献   

19.
Two nickel complexes supported by tridentate NS2 ligands, [Ni2(κN,S,S,S′‐NPh{CH2(MeC6H2R′)S}2)2] ( 1 ; R′=3,5‐(CF3)2C6H3) and [Ni2(κN,S,S,S′‐NiBu{CH2C6H4S}2)2] ( 2 ), were prepared as bioinspired models of the active site of [NiFe] hydrogenases. The solid‐state structure of 1 reveals that the [Ni2(μ‐ArS)2] core is bent, with the planes of the nickel centers at a hinge angle of 81.3(5)°, whereas 2 shows a coplanar arrangement between both nickel(II) ions in the dimeric structure. Complex 1 electrocatalyzes proton reduction from CF3COOH at ?1.93 (overpotential of 1.04 V, with icat/ip≈21.8) and ?1.47 V (overpotential of 580 mV, with icat/ip≈5.9) versus the ferrocene/ferrocenium redox couple. The electrochemical behavior of 1 relative to that of 2 may be related to the bent [Ni2(μ‐ArS)2] core, which allows proximity of the two Ni???Ni centers at 2.730(8) Å; thus possibly favoring H+ reduction. In contrast, the planar [Ni2(μ‐ArS)2] core of 2 results in a Ni???Ni distance of 3.364(4) Å and is unstable in the presence of acid.  相似文献   

20.
5-Amino-4-arylazo-3-methyl-1-phenylpyrazole (aryl?=?C6H5,o-C6H4COOH,o-C6H4OH) and its complexes with Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) ions were synthesized. The complexes are in the ratio 1?:?1 and 1?:?2 (metal?:?ligand). Ligands and complexes were subjected to elemental analysis, IR, Raman, UV-Vis and 1H-NMR spectroscopy. The mass spectra of the ligands were discussed. Thermal analysis and magnetic measurements were carried out for the prepared complexes. The X-ray single crystal structure of [Ni(L1)2] was performed. The investigated pyrazole compounds coordinate as bidentate ligands through amino and azo nitrogens or tridentate through NNO. The molar conductance of the chelates is measured and reflected the non-electrolytic nature of the prepared complexes.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号