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1.
Electrochemical Synthesis of Copper Nitrile Complexes Electrochemical syntheses of copper nitrile complexes by anodic dissolution of copper and cathodic reduction of malonodinitrile in a one‐step reaction are reported. In the presence of different donors the following compounds are obtained and characterized analytically: {[Cu 2(μ‐CN) · (CH 3CN) 3]CH(CN) 2} n ( 1 ), {[Cu 2(μ‐CN)(PPh 3) 4]CH(CN) 2} n ( 2 ) and [Cu 2(μ‐CN)(phen) 2(PPh 3) 2]CH(CN) 2 ( 3 ). As a result of an X‐ray analysis, 3 proved to be an ionic binuclear complex in which the cyano‐bridged Cu I atoms have distorted tetrahedral coordination sphere. Both the CN group and the dicyanomethanid anion are disordered about centres of inversion. 相似文献
2.
Summary The rhodium(I) carbonyl compounds [Rh(CO)L 22] [BF 4]. 1/2CH 2Cl nn2 (L = PPh 2 or AsPh 3) react with the nucleophiles OMe −, RCOO − (R = Me, Et) under nitrogen to form [Rh(OR)(CO)L 2] ( 1)–( 2) and [Rh(OOCR)(CO)L 2] ( 7)–( 10), respectively. Addition of [Rh(CO) 2(PPh 3) 2]-[BF 4] to OMe − under nitrogen produces [Rh(COOMe)-(CO) (PPh 3) 2]-MeOH ( 3), whilst reactions of [Rh(CO)-(PPh 3) 2] [BF 4]·1/2CH 2Cl 2 and [Rh(CO) 2(PPh 3) 2] [BF 4] with OR - (R = Me, Et or n-Pr) in the presence of CO produce [Rh(COOR)(CO) 2(PPh 3) 2] ( 4)–( 6). The products have been characterised by i.r., 1H, 31P, 13Cn.m.r. spectroscopy and elemental analysis. 相似文献
3.
In this study, {[Cu 2(µ-HCO 2) 4](µ-Mepyrz)} n ( 1), [Cu 2(µ-HCO 2) 4(Mepyrz) 2] ( 2), {[Cu 2(µ-AcO) 4](µ-Mepyrz)} n ( 3), [Cu 2(µ-AcO) 4(Mepyrz) 2] ( 4), [Cu 2(µ-AcO) 4(2,3-Me 2pyrz) 2] ( 5), [Cu 2(µ-AcO) 4(2,6-Me 2pyrz) 2] ( 6), and {[Cu 2(µ-AcO) 4](µ-2,5-Me 2pyrz)} n ( 7) have been synthesized and characterized by chemical analysis and electronic spectroscopy. Compounds 2, 4, 5, and 6, characterized by single-crystal X-ray diffraction, are composed of molecular dimers based on a paddle-wheel motif with two coppers, four syn–syn carboxylates, and two ligands coordinated to copper in the axial positions. In 7, chains of [Cu 2(µ-AcO) 4] dimers with 2,5-Me 2pyrz as bridging ligands are formed. Magnetic properties and electron paramagnetic resonance results of the compounds are also described. 相似文献
4.
Reactions of [ReX 2( η 2-N 2COPh-N′,O)(PPh 3) 2] with 3-methylbenzonitrile give two iso-structural complexes, [ReX 2(N 2COPh)(CH 3PhCN)(PPh 3) 2] (X?=?Cl, Br). The crystal and molecular structures of [ReCl 2(N 2COPh)(CH 3PhCN)(PPh 3) 2] ( 1) and [ReBr 2(N 2COPh)(CH 3PhCN)(PPh 3) 2]?·?CH 2Cl 2 ( 2) were determined. The electronic structures were examined with density functional theory (DFT). The spin-allowed electronic transitions were calculated with the time-dependent DFT method, and the UV-Vis spectrum has been discussed. 相似文献
5.
Hydrothermal reactions of CuCN, K 3[Fe(CN) 6] with 2,2′-bipyridine, 1,10-phenanthroline or 2,6- bis(1,2,4-triazolyl)pyridine (btp) afford three coordination polymers, [Cu 7(CN) 7(bipy) 2] n ( 1), [Cu 2(CN) 2(phen)] n ( 2) and [Cu 3(CN) 3(btp)] n ( 3). Complex 1 displays 1D polymeric ribbons which are assembled through Cu ··· Cu and π–π stacking interactions into a 3D framework. Complex 2 shows a 1D zigzag chain structure in which phen is a side ligand. In 3, the copper cyanide 2D polymeric networks are connected by tridentate btp to form a 3D metal-organic framework. These coordination polymers exhibit strong fluorescent emissions in the solid state. 相似文献
6.
The synthesis of tricyanomethyl copper complexes has been achieved by anodic dissolution of a sacrificial copper metal and cathodic reduction of 1, 1, 3, 3‐tetracyanopropane in acetonitrile, in the presence of triphenylphosphane used as coligand. The electrogenerated tetracyanopropyl radical anion is not stable and undergoes a cleavage leading to the tricyanomethyl anion and acrylonitrile which is electropolymerized at the cathode. The reaction solution gives a neutral dimeric binuclear copper(I) complex, bis{(μ‐ tricyanomethanido)bis(triphenylphosphane)copper(I)} [Cu(μ‐C(CN) 3)(PPh 3) 2] 2 ( 1 ). A second product of the synthesis reacts with 1, 10‐phenanthroline to give bis{cis‐(μ‐cyano)bis(triphenylphos‐phane)bis(phenanthroline)dicopper(I)}‐tricyanomethanide‐tetrafluoroborate‐diacetonitrile [cis‐{Cu 2(μ‐CN)(Phen) 2(PPh 3) 2}] 2[C(CN) 3] · BF 4 · 2CH 3CN ( 2 ). The crystal structures of 1 and 2 were determined by X‐ray analysis. 相似文献
7.
The interaction between the components of a catalytic system Pd(acac)(C 3-acac)PPh 3+ nPPh 3+ mBF 3OEt 2(where n= 1–4, m= 0.25–4, and acac is the acetylacetonate ligand) in benzene is examined by UV and IR spectroscopy. With a relative excess of PPh 3( n> m), acacH and [Pd(acac)(PPh 3) 2] +BF –
4were the main products, whereas BF 2acac and a polynuclear complex of PdF 2with PPh 3also containing Pd 2+(BF –
4) 2units were formed with a relative excess of BF 3OEt 2( n< m). 相似文献
8.
The methylation product of the reaction between [Pt 2(µ-S) 2(PPh 3) 4] and MeI in diethyl ether has been reinvestigated using positive-ion electrospray mass spectrometry and found to be contaminated with the dimethylated iodide-containing complex [Pt 2(µ-SMe) 2(PPh 3) 3I] +, which is believed to be formed early in the reaction. New, facile routes to the monomethylated complex [Pt 2(µ-S)(µ-SMe)(PPh 3) 4] + have been developed using mild methylating agents. Heating [Pt 2(µ-S) 2(PPh 3) 4] in neat dimethyl methylphosphonate results in rapid and selective conversion to [Pt 2(µ-S)(µ-SMe)(PPh 3) 4] +; methylation with Me 3S +OH ? in refluxing methanol also affords pure [Pt 2(µ-S)(µ-SMe)(PPh 3) 4] +, isolated as its hexafluorophosphate salt. The X-ray structure of the previously reported complex [Pt 2(µ-SMe) 2(PPh 3) 2I 2] has also been undertaken. 相似文献
9.
A series of cationic/neutral copper (I) complexes, [Cu 2(Hbmb)(PPh 3) 4] (BF 4) 2 ( 1a ), [Cu 2(Hbmb)(DPEPhos) 2](BF 4) 2 ( 2a ), [Cu 2(Hbmb)(Xantphos) 2](BF 4) 2 ( 3a ), [Cu 2(bmb)(PPh 3) 4] ( 1b ), [Cu 2(bmb)(DPEPhos) 2] ( 2b ), [Cu 2(bmb)(Xantphos) 2] ( 3b ) (Hbmb = 1,4-bis (1H-benzimidazol −2-yl)benzene, PPh 3 = triphenylphosphine, DPEPhos = bis[2-(diphenylphosphino)-phenyl]ether, Xantphos =4,5-bis (diphenylphosphino)-9,9′-dimethyl-xanthene), have been synthesized and characterized by IR, TGA, XRD and X-ray crystal structure analysis. The structural analysis reveals that each Cu + in all complexes adopts an almost ideal trigonal planar geometry, with three coordinate NP 2, and the C-H···π and π···π interactions are observed in the packing structures. DFT studied indicate the ingredients of the HOMOs and LUMOs for neutral copper (I) complexes 1b , 2b and 3b are different from cationic copper (I) complexes 1a , 2a and 3a , in accordance with the distribution of Mülliken atomic charges. Meanwhile, neutral copper (I) complexes 1b , 2b and 3b have fascinating broad blue-green emission bands at room temperature, while cationic copper (I) complexes 1a , 2a and 3a exhibit the existence of multiple emission peaks. Furthermore, the maximum phosphorescent lifetime and quantum yield at room temperature, for all copper (I) complexes, are 1143 μs and 8.82%, respectively. In addition, in order to measure the practical application of these complexes, the selection of complex 1b is used to fabricate the LED, which emits a bright warm-white light. 相似文献
10.
Reaction of [(η 5-Cp)Ru(PPh 3) 2Cl] ( 1) with excess para-amino- N-(pyrid-2-ylmethylene)-phenylamine ligand (app) in methanol in the presence of NH 4BF 4 leads to the formation of [η 5-CpRu(PPh 3)(aap)]BF 4 ( 6BF 4). Similarly, [(η 5-ind)Ru(PPh 3) 2(CH 3CN)]BF 4 ( 4BF 4) and [(η 5-Cp*)Ru(PPh 3) 2(CH 3CN)]BF 4 ( 5BF 4) react with app to yield the cationic complexes [(η 5-ind)Ru(PPh 3)(app)]BF 4 ( 7BF 4) and [(η 5-Cp*)Ru(PPh 3)(app)]BF 4 ( 8BF 4), respectively. The complexes were characterized by analysis and spectroscopic data. The structure of a representative complex ( 6BF 4) was established by single-crystal X-ray methods. 相似文献
11.
A Ligand-Directed strategy has been adopted to synthesize three novel Copper(І) coordination polymers, [Cu 2(bpe)(N 3) 2]
n
(1), [Cu 2(bpy)(N 3) 2]
n
(2), and [Cu 4(py)(N 3) 4]
n
(3), by the reactions of NaN 3 with bpe, bpy and py (bpe = 1,2-trans-(4-pyridyl)ethene, bpy = 4,4′-bipyridine, py = pyrazine) in the presence of H 3PO 3 under hydrothermal conditions, which proved that the length of ligands had subtle effects on overall network and the coordination
mode of azide. 相似文献
12.
Chalcogenoniobates as Reagents for the Synthesis of New Heterobimetallic Niobium Coinage Metal Chalcogenide Clusters In the presence of phosphine chalcogenoniobates such as Li 3[NbS 4] · 4 CH 3CN ( I ), (NEt 4) 4[Nb 6S 17] · 3 CH 3CN ( II ) and (NEt 4) 2[NbE′ 3(E tBu)] ( III a : E′ = E = S; III b : E = Se, E′ = S; III c : E = E′ = Se) respectively react with copper and gold salts to give a number of new heterobimetallic niobium copper(gold) chalcogenide clusters. These clusters show metal chalcogenide units already known from the complex chemistry of the tetrachalcogenometalates [ME 4] n– (M = V, n = 3, E = S; M = Mo, W, n = 2, E = S, Se). The compounds 1 – 8 owe a central tetrahedral [NbE 4] structural unit, which coordinates η 2 from two to five coinage metal atoms, employing the chalcogenide atoms of the [NbE 4] edges. The compounds 9 – 11 have a [M′ 2Nb 2E 4] (M′ = Cu, Au) heterocubane unit in common, involving a metal metal bond between the niobium atoms, while the compounds 12 and 13 show a complete and 14 an incomplete [M′ 3NbE 3X] heterocubane structure (X = Cl, Br). 15 consists of a Cu 6Nb 2 cube with the six planes capped by μ 4 bridging selenide ligands forming an octahedra. The compounds 1 – 15 are listed below: (NEt 4) [Cu 2NbSe 2S 2(dppe) 2] · 2 DMF ( 1 ), [Cu 3NbS 4(PPh 3) 4] ( 2 ), [Au 3NbSe 4(PPh 3) 4] · Et 2O ( 3 ), [Cu 4NbS 4Cl(PCy 3) 4] ( 4 ), [Cu 4NbS 4Cl(P tBu 3) 4] · 0,5 DMF ( 5 ), [Cu 4NbSe 4(NCS)(P tBu 3) 4] · DMF ( 6 ), [Cu 4NbS 4(NCS)(dppm) 4] · Et 2O ( 7 ), [Cu 5NbSe 4Cl 2‐ (dppm) 4] · 3 DMF ( 8 ), [Cu 2Nb 2S 4Cl 2(PMe 3) 6] · DMF ( 9 ), [Au 2Nb 2Se 4Cl 2(PMe 3) 6] · DMF ( 10 ), (NEt 4) 2[Cu 3Nb 2S 4(NCS) 5(dppm) 2(dmf)] · 4 DMF ( 11 ), [Cu 3NbS 3Br(PPh 3) 3(dmf) 3]Br · [CuBr(PPh 3) 3] · PPh 3 · OPPh 3 · 3 DMF ( 12 ), [Cu 3NbS 3Cl 2(PPh 3) 3(dmf) 2] · 1.5 DMF ( 13 ), (NEt 4)[Cu 3NbSe 3Cl 3(dmf) 3] ( 14 ), [Cu 6Nb 2Se 6O 2(PMe 3) 6] ( 15 ). The structures of these compounds were obtained by X‐ray single crystal structure analysis. 相似文献
13.
Three new coordination polymers [Co(bimb) 2(NCS) 2] n ( 1), {[Co(bimb) 2(dca) 2]?·?CH 3CN} n ( 2) and [Cu(bimb) 2(NO 3) 2] n ( 3) (bimb?=?1,4- bis(imidazol-1-yl)butane, dca?=?dicyanamide) were synthesized and characterized. In 1, each Co(II) links two Co(II)'s by double bimb ligands and extends to form a one-dimensional chain containing the Co 2(bimb) 2 22-membered metallocycle. 2 and 3 are two-dimensional (4, 4) networks linked by bimb bridges. The conformations of the bimb ligands in 1, 2 and 3 are analyzed. 相似文献
14.
3D La III and 2D Cu II coordination polymers with 5-nitroisophthalate anions, [La 2(μ-Nip)(μ-SO 4) 2(H 2O) 5] n ( 1) and {[Cu 3(μ-OH) 2(μ-Nip) 2(μ-H 2O) 2] ·?2H 2O} n ( 2), have been synthesized, characterized and studied by X-ray crystallography. The La atoms have eight–coordinate geometries in distorted square antiprism environments and the Cu atoms have five- and six–coordinate geometries with distorted square pyramidal and octahedral environments. Self-assembly of these compounds in the solid state occurs through coordination and hydrogen bonding. 相似文献
15.
以3,5-二甲(丙)基-4-氨基-1,2,4-三唑为配体,与CuI在H 2O/MeCN混合溶剂热合成了2个构型不同的Cu 4I 4超分子化合物{[Cu 2(aadmtrz) I 2]·CH 3CN} n( 1)和[Cu 2(dptrz) I] n( 2)(aadmtrz=4-((1-氨乙基)-氨基)-3,5-二甲基-1,2,4-三唑,dptrz=3,5-二丙基-1,2,4-三唑),并进行了元素分析,红外,X射线粉末衍射及单晶衍射等表征。2个配合物中Cu 4I 4构型不同,配合物 1中,Cu 4I 4簇连结成一个8环椅式-椅式结构,通过配体连接成(4,4)二维菱形格子结构;而配合物 2中,Cu 4I 4簇呈畸变的立方烷结构,构成了含有19.5%孔隙率三维孔洞聚合物,其结构可简化为(3,4)-连接的拓朴结构。同时,在常温下研究了2个配合物的固体荧光性质。 相似文献
16.
The catecholase activity of the dicopper(II) complexes [Cu 2(L 1)( μ‐OCH 3)(NCCH 3) 2](PF 6) 2·H 2O·CH 3CN ( 1 ), [Cu 2(L 2)( μ‐OH)(MeOH)(NCCH 3)](BF 4) 2 ( 2 ), [Cu 2(L 3)( μ‐OMe)(NCCH 3) 2](BF 4) 2·2CH 3CN·H 2O ( 3 ), [Cu 2(L 2)( μ‐OAc) 2]BF 4·H 2O ( 4 ), [Cu 2(L 4)( μ‐OAc) 2]ClO 4 ( 5 ) and [Cu 2(L 5)( μ‐OMe)(NCCH 3) 3(OH 2)](ClO 4) 2·2CH 3OH·CH 3CN ( 6 ) consisting of varying para‐substituted phenol ligands HL 1 = 4‐trifluoromethyl‐2,6‐bis((4‐methylpiperazin‐1‐yl)methyl)phenol, HL 2 = 4‐bromo‐2,6‐bis((4‐methyl‐1,4‐diazepan‐1‐yl)methyl)phenol, HL 3 = 4‐bromo‐2‐((4‐methyl‐1,4‐diazepan‐1‐yl)methyl)‐6‐((4‐methylpiperazin‐1‐yl)methyl)phenol, HL 4 = 2,6‐bis((4‐methylpiperazin‐1‐yl)methyl)‐4‐nitrophenol and HL 5 = 4‐ tert‐butyl‐2,6‐bis((4‐methylpiperazin‐1‐yl)methyl)phenol was studied. The main difference within the six complexes lies in the individual copper–copper separation that is enforced by the chelating side arms of the phenolate ligand entity and more importantly in the exogenous bridging solvent, hydroxide, methanolate or acetate ions. The distance between the copper cores varies from 2.94Å in 1 to 3.29Å in 5 . The catalytic activity of the complexes 1 – 6 towards the oxidation of 3,5‐di‐ tert‐butylcatechol was determined spectrophotometrically by monitoring the increase of the 3,5–di‐ tert‐butylquinone characteristic absorption band at about 400 nm over time saturated with O 2. The complexes are able to oxidize the substrate 3,5‐di‐ tert‐butylcatechol to the corresponding o‐quinone with distinct catalytic activity (k cat between 92 h ?1 and 189 h ?1), with an order of decreasing activity 6 > 5 > 1 , 2 , 4 ≥ 3 . A kinetic treatment of the data based on the Michaelis‐Menten approach was applied. A correlation of the catecholase activities with the variation of the para‐ substituents as well as other effects resulting from the copper core distances is discussed. [Cu 2(L 5)( μ‐OMe)(NCCH 3) 3(OH) 2](ClO 4) 2·2CH 3OH·CH 3CN ( 6 ) exhibited the highest activity of the six complexes as a result of its high turnover rate. 相似文献
17.
Treatment of [RuCl 2(PPh 3) 3] with 2 equiv. Himt MPh (Himt MPh?=?1-(4-methyl-phenyl)-imidazole-2-thione) in the presence of MeONa afforded cis-[Ru( κ 2- S, N-imt MPh) 2(PPh 3) 2] ( 1), while interaction of [RuCl 2(PPh 3) 3] and 2 equiv. Himt MPh in tetrahydrofuran (THF) without base gave [RuCl 2( κ 1- S-Himt MPh) 2(PPh 3) 2] ( 2). Treatment of [RuHCl(CO)(PPh 3) 3] with 1 equiv. Himt MPh in THF gave [RuHCl( κ 1- S-Himt MPh)(CO)(PPh 3) 2] ( 3), whereas reaction of [RuHCl(CO)(PPh 3) 3] with 1 equiv. of the deprotonated [imt MPh] ? or [imt NPh] ? (imt NPh?=?1-(4-nitro-phenyl)-2-mercaptoimidazolyl) gave [RuH( κ 2- S, N-imt RPh)(CO)(PPh 3) 2] (R?=?M 4a, R?=?N 4b). The ruthenium hydride complexes 4a and 4b easily convert to their corresponding ruthenium chloride complexes [RuCl( κ 2- S, N-imt MPh)(CO)(PPh 3) 2] ( 5a) and [RuCl( κ 2- S, N-imt NPh)(CO)(PPh 3) 2] ( 5b), respectively, in refluxing CHCl 3 by chloride substitution of the RuH. Photolysis of 5a in CHCl 3 at room temperature afforded an oxidized product [RuCl 2( κ 2- S, N-imt MPh)(PPh 3) 2] ( 6). Reaction of 6 with excess [imt MPh] ? afforded 1. The molecular structures of 1·EtOH, 3·C 6H 14, 4b·0.25CH 3COCH 3, and 6·2CH 2Cl 2 have been determined by single-crystal X-ray crystallography. 相似文献
18.
The cyclotriveratrylene-type ligands (±)-tris(iso-nicotinoyl)cyclotriguaiacylene L1 (±)-tris(4-pyridylmethyl)cyclotriguaiacylene L2 and (±)-tris{4-(4-pyridyl)benzyl}cyclotriguaiacylene L3 all feature 4-pyridyl donor groups and all form coordination polymers with Cu I and/or Cu II cations that show a remarkable range of framework topologies and structures. Complex [Cu I
4Cu II
1.5(L1) 3(CN) 6]·CN· n(DMF) 1 features a novel 3,4-connected framework of cyano-linked hexagonal metallo-cages. In complexes [Cu 3(L2) 4(H 2O) 3]·6(OTf)· n(DMSO) 2 and [Cu 2(L3) 2Br 2(H 2O)(DMSO)]·2Br· n(DMSO) 3 capsule-like metallo-cryptophane motifs are formed which linked through their metal vertices into a hexagonal 2D network of (4 3.12 3)(4 2.12 2) topology or a coordination chain. Complex [Cu 2(L1) 2(OTf) 2(NMP) 2(H 2O) 2]·2(OTf)·2NMP 4 has an interpenetrating 2D 3,4-connected framework of (4.6 2.8)(6 2.8)(4.6 2.8 2) topology with tubular channels. Complex [Cu(L1)(NCMe)]·BF 4·2(CH 3CN)·H 2O 5 features a 2D network of 6 3 topology while the Cu II analogue [Cu 2(L1) 2(NMP)(H 2O)]·4BF 4·12NMP·1.5H 2O 6 has an interpenetrating (10,3)- b type structure and complex [Cu 2(L2) 2Br 3(DMSO)]·Br· n(DMSO) 7 has a 2D network of 4.8 2 topology. Strategies for formation of coordination polymers with hierarchical spaces emerge in this work and complex 2 is shown to absorb fullerene-C 60 through soaking the crystals in a toluene solution. 相似文献
19.
Cationic methyl complex of rhodium(III), cis-[Rh(Acac)(PPh 3) 2(CH 3)(Py)][BPh 4] ( 1) as a single isomer with Py in the trans to PPh 3 position, is formed upon the reaction of cis-[Rh(Acac)(PPh 3) 2(CH 3)(CH 3CN)][BPh 4] with pyridine in methylene chloride solution.Complex 1 was characterized by elemental analysis and by 31P{ 1H} and 1H NMR spectra.Cationic pentacoordinate acetyl complexes, trans-[Rh(Acac)(PPh 3) 2(COCH 3)][BPh 4] ( 2) and trans-[Rh(BA)(PPh 3) 2(COCH 3)][BPh 4] ( 3), are prepared by action of carbon monoxide on cis-[Rh(Acac)(PPh 3) 2(CH 3)(CH 3CN)][BPh 4] and cis-[Rh(BA)(PPh 3) 2(CH 3)(CH 3CN)][BPh 4], respectively, in methylene chloride solutions.Complexes 2 and 3 were characterized by elemental analysis and by IR, 31P{ 1H}, 13C{ 1H} and 1H NMR. According to NMR data, 2 and 3 in solution are non-fluxional trigonal bipyramids with β-diketonate and acetyl ligands in the equatorial plane and axial phosphines.In solutions, 2 and 3 gradually isomerize into octahedral methyl carbonyl complexes trans-[Rh(Acac)(PPh 3) 2(CO)(CH 3)][BPh 4] ( 4) and trans-[Rh(BA)(PPh 3) 2(CO)(CH 3)][BPh 4] ( 5), respectively.Complexes 4 and 5 were characterized by IR, 31P{ 1H}, 13C{ 1H} and 1H NMR, without isolation.Upon the action of PPh 3 on cis-[Rh(Acac)(PPh 3) 2(CH 3)(CH 3CN)][BPh 4] and cis-[Rh(BA)(PPh 3) 2(CH 3)(CH 3CN)] [BPh 4], reductive elimination of the methyl ligand as a phosphonium salt, [CH 3PPh 3][BPh 4], occurs to give square planar rhodium(I) complexes [Rh(Acac)(PPh 3) 2] and[Rh(BA)(PPh 3) 2], respectively. The reaction products were identified in the reaction mixtures by 31P{ 1H} and 1H NMR. 相似文献
20.
Two cyanide-bridged heterometallic FeIII–MnII complexes with formula {[Mn(bipy)(H2O)]2[Fe(2-CH3im)(CN)5]2}n·nCH3OH·4nH2O (2) (bipy?=?2,2′-bipyridine) and {[Mn(MAC)][Fe(2-CH3im)(CN)5]}n·nDMF·3nH2O (3) (MAC?=?2,13-dimethyl-3,6,9,12,18-pentaazabicyclo-[12.3.1]octadeca-1(18),2,12,14,16-pentaene) have been successfully synthesized by assembling a newly designed pentacyanoiron(III) precursor [PPh4]2[Fe(CN)5(2-CH3im)]·2CH3OH (1) and two Mn(II) compounds containing bulky ancillary organic ligands as segments, and characterized by elemental analysis, infrared (IR) spectroscopy, and X-ray structure determination. X-ray diffraction analysis revealed one-dimensional (1D) ladder-like double or linear single infinite-chain structures for complex 2 and 3, respectively, indicating the obvious steric influence of the auxiliary ligand(s) on the structural type. Experimental and theoretical investigations on the magnetic properties of the complexes showed the antiferromagnetic coupling between the cyanide-bridged low-spin Fe(III) ion and high-spin Mn(II) ion. 相似文献
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