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1.
Reaction of the ligands diphenylphosphinylacetic acid Ph2P(O)CH2COOH (1) and 2-(tert-butylthio)phenyldiphenylphosphine oxide Ph2P(O)C6H4tBuS (2) with “MoO2Cl2”, resulted in two complexes MoO2Cl2Ph2P(O)CH2COOH (3) and MoO2Cl2Ph2P(O)C6H4tBuS(O) (4). Complexes 3 and 4 were isolated and analysed by 1H NMR, 31P NMR and X-ray crystallography. Complex 3 crystallised with a molecule of the free ligand in a 1:1 ratio (3·1) and complex 4 crystallised with molecules of the solvent CH2Cl2 within the unit cell in a 2:1 ratio (4·0.5CH2Cl2). Tetrameric arrangements comprised of hydrogen bonds were observed in complexes 1 and 3. Complex 4 exhibited a seven-membered ring structure owing to the oxidation of the sulphide in 2 to sulphoxide and coordination of this ligand via the oxygen atoms to the molybdenum atom. 相似文献
2.
Nicholas F. Brennan Simon Lotz Marilé Landman Mike J. Green 《Inorganica chimica acta》2008,361(11):3042-3052
Substitution of thf ligands in [Cr(thf)3Cl3] and [Cr(thf)2(OH2)Cl3] was investigated. 2,2′-Bipyridine (bipy) was reacted with [Cr(thf)3Cl3] to form [Cr(bipy)(thf)Cl3] (1), which was subsequently reacted with water to give [Cr(bipy)(OH2)Cl3] (2). Reaction of 1 with acetonitrile (CH3CN), pyridine (py) and pyridine derivatives to form [Cr(bipy)(L)Cl3] (L = CH3CN 3, py 4 and 4-pyR with R = NH25, But6 and Ph 7). In addition, the substitution of bipy in [Cr(thf)3Cl3] was followed by 1H NMR spectroscopy at room temperature, which showed completion of the reaction in ca. 100 min. Complex 2 was characterised by single crystal X-ray diffraction. The theoretical powder diffraction pattern of 2 was compared to the experimentally obtained powder X-ray diffraction pattern, and shows excellent agreement. The dimer [Cr2(bipy)2Cl4(μ-Cl)2] was cleaved asymmetrically to give the anionic complex [Cr(bipy)Cl4]− (8) and [Cr(bipy)2Cl2]+ (9). Complexes 8 and 9 were characterised by single crystal X-ray diffraction. 相似文献
3.
Pasquale Mura Mercedes Camalli Chiara Gabbiani 《Journal of inorganic biochemistry》2010,104(2):111-117
A novel ruthenium(II) compound, trans-cis-cis-[Ru(II)Cl2(DMSO)2(2-amino-5-methyl-thiazole)2], (I), PMRu52 hereafter, that may be obtained from the previously described (cis and trans)-[Ru(II)Cl2(DMSO)4] complexes, was designed, synthesized and characterised. The single crystal X-ray structure shows a roughly regular octahedral environment for the ruthenium(II) center with the two chloride ligands in trans and the other two pairs of identical ligands in cis. The behaviour of PMRu52 in phosphate buffer, at pH = 7.4, was characterised spectroscopically as well as its interactions with a few representative biomolecules. Tight ruthenium binding to serum albumin was established by joint use of spectroscopic and separation methods. Afterward, the reactions of PMRu52 with the model proteins ubiquitin and cytochrome c were monitored through electrospray ionisation mass spectrometry (ESI-MS) methods: the formation of metallodrug-protein adducts was documented in detail and the fragmentation patterns of PMRu52 were defined. Finally, the ability of PMRu52 to affect the activity of cathepsin B, a well known cysteine protease, was evaluated in vitro and a pronounced enzyme inhibition highlighted, with an IC50 value of 5.5 μM. This latter finding is of particular interest as cathepsin B constitutes an attractive “druggable” target for cancer, rheumatoid arthritis and other important diseases. 相似文献
4.
D CourtneyN.L Cromhout D CunninghamJ.F Gallagher A.R Manning P McArdleS.I Pratt 《Inorganica chimica acta》2002,327(1):98-107
The iron hydrido complex HFe(CO)2{P(OPh)3}{(PhO)2POC6H4} (1), was rapidly deprotonated by DBU or [BzMe3N][OH] in THF to afford the new carbonyl iron anion [Fe(CO)2{P(OPh)3}{(PhO)2POC6H4}]− ([2]−), containing an ortho-metallated triphenyl phosphite ligand. Complex [2]− reacted with triorganostannyl and plumbyl salts and with halogens to give the octahedral FeII compounds Fe(CO)2{P(OPh)3}{(PhO)2POC6H4}(X) (X=SnPh3, 3; SnMe3, 4; PbPh3, 5; PbMe3, 6; Cl, 7; Br, 8; I, 9). The Group 14 complexes 3-6 were obtained in one isomeric form in which the PIII-donor atoms are mutually cis, the carbonyl ligands are cis and the P(OPh)3 and MR3 (M=Sn, Pb; R=Ph, Me) groups are trans as determined by solution-state IR, 31P and 13C NMR spectroscopic data. This geometry was confirmed for 3 by a single crystal X-ray diffraction study. The halide complexes, however, were obtained as a mixture of isomers. The major isomer (7, X=Cl; 8a, X=Br; 9a, X=I) has cis P atoms, trans CO groups and the halide located trans to the phosphorus atom of the ortho-metallated phosphite ligand. The structure of 9a was confirmed by an X-ray diffraction study. Two other isomers, designated 8b (X=Br) and 9b (X=I), with cis P atoms and cis CO groups were isolated from the reactions of [2]− with Br2 and I2, respectively. The structure of the latter was established by X-ray crystallography and is related to 9a by exchange of the P(OPh)3 ligand and a carbonyl group such that the metal-bound C atom of the five-membered metallacycle is trans to CO. The stereo-geometry of 8b could not be unambiguously assigned from the spectroscopic data; however, two of the seven possible geometric isomers were suggested as plausible structures. 相似文献
5.
Hsiao-Yun Weng 《Inorganica chimica acta》2004,357(5):1369-1373
Reaction of Mo2(O2CCH3)2(DMepyF)2 (HDMepyF=N,N′-di(6-methyl-2-pyridyl)formamidine) with HBF4 in CH2Cl2/CH3CN afforded the complex trans-[Mo2(H2DMepyF)2(CH3CN)4](BF4)6 (1), which crystallized in two forms, trans-[Mo2(H2DMepyF)2(CH3CN)4](ax-CH3CN)2(BF 4)6 · 2CH3CN (1a), and trans- [Mo2(H2DMepyF)2(CH3CN)4](ax-BF4) 2(BF4)4 · 2CH3CN (1b). The molecular structures of complexes (1) consist of two quadruply bonded molybdenum atoms, which are spanned by two trans-bridging formamidinate ligands and coordinated by four trans-CH3CN. Each H2DMepyF+ ligand adopts an s-cis,s-cis- conformation. The difference between 1a and 1b is that complex 1a contains two CH3CN molecules as axial ligands, while 1b contains two BF4− anions as axial ligands. Complex 1 is the first dimolybdenum complex containing a pair of trans bridging ligands and two pairs of trans-CH3CN ligands. 相似文献
6.
Mikhail N. Bochkarev Georgy V. Khoroshenkov Dmitry M. Kuzyaev Anatoly A. Fagin Mikhail E. Burin Georgy K. Fukin Eugeny V. Baranov Alexander A. Maleev 《Inorganica chimica acta》2006,359(10):3315-3320
It was found that the lanthanide diiodides LnI2 (1) (Ln = Nd, Sm, Eu, Dy, Tm, Yb) are dissolved in isopropylamine (IPA) without redox transformations. Stability of the formed solutions decreases in a row Eu ≈ Yb > Sm > Tm > Dy > Nd. Removing of a solvent in vacuum leaves complexes LnI2(IPA)x (2) (Nd, x = 5; Sm, Eu, Dy, Tm, Yb, x = 4) as crystalline colored solids. Stability of 2-Nd,Dy,Tm is higher than that of known THF or DME coordinated salts. Divalent state of metal in the products is confirmed by data of UV-Vis spectroscopy, magnetic measurements and their chemical behavior. Structure of 2-Eu and 2-Tm was established by X-ray diffraction analysis. Oxidation of 2-Nd,Dy in IPA affords amine-amides (PriNH)Ln(IPA)y (3) (Nd, y = 4; Dy, x = 3). n-Propylamine also dissolves the iodides 1-Sm,Eu,Dy,Tm,Yb but stability of the solutions is significantly lower. 1-Nd vigorously reacts with PrnNH2 even at −30 °C which hampers the formation of the solution. 相似文献
7.
Yan-Gong Han 《Inorganica chimica acta》2011,365(1):414-418
Metathesis reaction between equimolar amount of [Et4N][GaCl4] and Na2edt in methanol resulted in the formation of the dichloro complex [Et4N][Ga(edt)Cl2] (1), whereas reaction of [Et4N][GaCl4] with two equivalents of Na2edt in methanol gave the complex [Et4N][Ga(edt)2] (2) which can act as a metalloligand. Treatment of 2 with M(PPh3)2NO3 in DMF/CH2Cl2 afforded the heterobimetallic complexes [Ga(edt)2M-(PPh3)2] (M = Cu 3, Ag 4) in moderate yields. The structures of 1-4 were determined by single-crystal X-ray diffraction analyses. Both [Ga(edt)Cl2]− and [Ga(edt)2]− anions have a distorted tetrahedral geometry. The former consists of one five-membered ring formed by chelating dithiolate and two terminal chloride atoms while the latter consists of two five-membered rings formed by two the chelating dithiolates. Complexes 3 and 4 consist of metalloligand [Ga(edt)2]− anion chelated to [M(PPh3)2]+via the sulfur atoms. Both tetrahedrally coordinated Ga and Cu(Ag) atoms are bridged by two sulfur atoms, forming a planar “GaS2M” (M = Cu, Ag) core. Thermogravimetry analysis revealed that heterobimetallic complexes 3 and 4 decomposed to give the corresponding ternary metal sulfide materials. 相似文献
8.
Tong Ren Damon A. Parrish Jeffrey R. Deschamps Guo-Lin Xu Martin H. Moore Steven K. Pollack A.P. Sattelberger 《Inorganica chimica acta》2004,357(4):1313-1316
The reaction between Os2(OAc)4Cl2 and Hap (Hap is 2-anilinopyridine) under prolonged refluxing conditions resulted in a new Os2(III) compound, Os2(ap)4Cl2 (1). The molecular structure of 1 was determined from a single crystal X-ray diffraction study, which revealed an Os-Os bond length of 2.396[1] Å, and a cis-(2,2) arrangement of the ap ligands. Also reported are magnetic, electrochemical and spectroscopic properties of 1. 相似文献
9.
Two novel monomeric [C18H17Cl3N2O2Fe] (1) and dimeric [C38H36N4O4Cl6Fe2] (2) Fe(III) tetradentate Schiff base complexes have been synthesized and their crystal structures have been determined by single crystal X-ray diffraction analysis. In complex (1) the Schiff base ligand coordinates toward one iron atom in a tetradentate mode and each iron atom is five coordinated with the coordination geometry around iron atom which can be described as a distorted square pyramid. The presence of a short (2.89 Å) non-bonding interatomic Fe···O distances between adjacent monomeric Fe(III) complexes results in the formation of a dimer. Structural analysis of compound (2) shows that the structure is a centrosymmetric dimer in which the six coordinated Fe(III) atoms are linked by μ-phenoxo bridges from one of the phenolic oxygen atoms of each Schiff base ligand to the opposite metal center. The variable-temperature (2-300 K) magnetic susceptibility (χ) data of these two compounds have been investigated. The results show that for both complexes Fe(III) centers are in the high spin configuration (S = 5/2) and indicate antiferromagnetic spin-exchange interaction between Fe(III) ions. The obtained results are briefly discussed using magnetostructural correlations developed for other class of iron(III) complexes. 相似文献
10.
Thomas Weyhermüller 《Inorganica chimica acta》2011,374(1):140-146
The tridentate unsymmetrical ligand N-(2-hydroxymethylphenyl)salicylideneimine H2L, derived from salicylaldehyde and 2-aminobenzylalcohol, with [ONO] donor atoms yields [L2FeIII2Cl2] (1) and [L6FeIII4] (2) complexes containing alkoxide bridges, which have been structurally characterized by X-ray diffraction. In complex 1, each ferric ion is five-coordinated with a distorted square-pyramidal geometry, the basal planes of which are symmetrically bridged by two alkoxide oxygen atoms. Analysis of the susceptibility data reveals antiferromagnetic interactions with an exchange parameter J = −15.8 cm−1 between the high-spin d5 ferric centers. The structure of 2 can be considered as “linear (2,2,2)” to specify the number of enolate oxygen atoms between four iron atoms. Variable-temperature magnetic susceptibility data are fitted to a “three-J” model, yielding pairwise antiferromagnetic exchange interactions, J12 = J34 = −13.4 cm−1, J13 = J24 = −7.1 cm−1, J23 = −14.9 cm−1, between the neighboring ferric centers; J14 is assumed to be negligible. Complex 2 has a complicated low-lying magnetic structure with a non-diamagnetic ground state. In addition, the Fe-O-Fe angles at the bridging ligands seem to be determinant for the strength of the antiferromagnetic interactions. 相似文献
11.
M.R. Pedrosa 《Inorganica chimica acta》2010,363(13):3158-3164
MoO2Cl2(L)2 [L = (R)-(+)-methyl-p-tolylsulfoxide (R-MeTolSO) (1), methyl-p-tolylsulfoxide (MeTolSO) (2), 2-benzenesulfinyl-1,1-diphenylethanol (BSDPE) (3), 1-benzenesulfinyl-2-methyl-2-propanol (BSMP) (4), benzenesulfinylmethyl 4-methylphenyl ketone (BSMMPK) (5)], and MoO2Cl2(L) [L = BSDPE (6), BSMP (7), BSMMPK (8), (S,S)-bis(p-tolylsulfinyl)methane (S,S-TolSOCH2SOTol) (9), bis(methylsulfinyl)methane (MeSOCH2SOMe) (10), bis(phenylsulfinyl)methane (PhSOCH2SOPh) (11)] have been synthesized by reacting a solution of MoO2Cl2(H2O)2 in diethyl ether with the corresponding ligand. The crystal and molecular structures of 1, 2, and 9 have been established by X-ray diffraction analysis. The ability of 1 and 9 as catalysts for the enantioselective reduction of sulfoxides to sulphides and the oxidation of sulphides to sulfoxides has been examined. 相似文献
12.
Palladium(II) and platinum(II) complexes with N-alkylpyridylpyrazole-derived ligands, 2-(1-ethyl-5-phenyl-1H-pyrazol-3-yl)pyridine (L1) and 2-(1-octyl-5-phenyl-1H-pyrazol-3-yl)pyridine (L2), cis-[MCl2(L)] (M = Pd(II), Pt(II)), have been synthesised. Treatment of [PdCl2(L)] (L = L1, L2) with excess of ligand (L1, L2), pyridine (py) or triphenylphosphine (PPh3) in the presence of AgBF4 and NaBPh4 produced the following complexes: [Pd(L)2](BPh4)2, [Pd(L)(py)2](BPh4)2 and [Pd(L)(PPh3)2](BPh4)2. All complexes have been characterised by elemental analyses, conductivity, IR and NMR spectroscopies. The crystal structures of cis-[PdCl2(L2)] (2) and cis-[PtCl2(L1)] (3) were determined by a single crystal X-ray diffraction method. In both complexes, the metal atom is coordinated by one pyrazole nitrogen, one pyridine nitrogen and two chlorine atoms in a distorted square-planar geometry. In complex 3, π-π stacking between pairs of molecules is observed. 相似文献
13.
Treatment of ‘RuCl3 · 3H2O’ with Ph2AsCH2AsPh2 (dpam) in hot EtOH gives either trans-[RuCl2(dpam-As,As′)(dpam-As)2] (1), or cis-[RuCl2(dpam-As,As′)2] (2), depending on the mole ratio. On exposure to light, solutions of 2 isomerise to trans-[RuCl2(dpam-As,As′)2] (3). Treatment of [RuCl2(PPh3)3] with two equivalents of dpam in CH2Cl2 gave a mixture of two products, from which trans-[RuCl2(PPh3) (dpam-As,As′)(dpam-As)] (4) was isolated by recrystallisation. The crystal structures of 1-4 are reported. Complexes 1-3 in CH2Cl2 undergo electrochemical oxidation to Ru(III), and the Ru(III) form of 2 undergoes isomerisation on the voltammetric timescale to the Ru(III) form of 3. 相似文献
14.
Ludovic Chahen 《Inorganica chimica acta》2005,358(12):3417-3422
The new aryl phosphinites PPh2OR (R = 2,4,6-Me3C6H2, 1; R = 2,6-Ph2C6H3, 2) have been prepared from chlorodiphenylphosphine and the corresponding phenols. In these ligands, the ortho-positions of the aromatic phosphite function are blocked by methyl and phenyl substituents, which allows coordination to metal centres without ortho-metallation. Thus, reaction with [PdCl2(cod)] leads to the complexes trans-[PdCl2(PPh2OR)2] (R = 2,4,6-Me3C6H2, 3; R = 2,6-Ph2C6H3, 4), while the reaction with [Rh2(CO)4Cl2] gives trans-[Rh(CO)Cl(PPh2OR)2] (R = 2,4,6-Me3C6H2, 5; R = 2,6-Ph2C6H3, 6). The single-crystal X-ray structure analyses of 3 and 5 confirm the trans-coordination of the new ligands in these square-planar complexes. 相似文献
15.
Two new rhenium(IV) mononuclear compounds of formula NBu4[ReBr4(OCN)(DMF)] (1) and (NBu4)2[ReBr(OCN)2(NCO)3] (2) (NBu4 = tetrabutylammonium cation, OCN = O-bonded cyanate anion, NCO = N-bonded cyanate anion and DMF = N,N-dimethylformamide) have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. 1 crystallizes in the monoclinic system with the space group P21/n, whereas 2 crystallizes in the triclinic one with as space group. In both complexes the rhenium atom is six-coordinated, in 1 by four Br atoms in the equatorial plane, and two trans-oxygen atoms, one of a DMF molecule and another one from a cyanato group, while in 2 by one bromide anion and five cyanate ligands, two of which are O-bonded and three N-bonded, forming a somewhat distorted octahedral surrounding. Magnetic susceptibility measurements on polycrystalline samples of 1 and 2 in the temperature range 1.9-300 K are interpreted in terms of magnetically isolated spin quartets with large values of the zero-field splitting (|2D| is ca. 41.6 and 39.2 cm−1 for 1 and 2, respectively). 相似文献
16.
Hui-Bo Zhou Shu-Ping Wang Dai-Zheng Liao Zong-Hui Jiang Peng Cheng 《Inorganica chimica acta》2006,359(2):533-540
Two new complexes, {[MnAu2(CN)4(NITpPy)2(H2O)2]}n (1) and {[Co(N(CN)2)2(NITpPy)2(H2O)2]}n (2), have been synthesized and characterized. The single-crystal X-ray analysis for the complexes 1 and 2 demonstrates that each M(II) (M = Mn or Co) ion assumes a distorted octahedral MN4O2 coordination polyhedron. Four nitrogen atoms come from the cyanide groups and the pyridyl rings in a common plane, and two oxygen atoms come from the H2O molecules in trans-positions. The structures of complexes 1 and 2 illustrate that aurophilicity and/or hydrogen bonding interactions play important roles in increasing dimensionality. Magnetic investigations on complexes 1 and 2 show the presence of weak antiferromagnetic interactions. 相似文献
17.
The mono-substituted amine derivatives [Ir4(CO)11L] (L = pyridine (1), 4-methylpyridine (2), 4-ter-butyl pyridine (3), 3,5-dimethylpyridine (4), 3,4-dimethylpyridine (5)) were obtained by the reaction of [Ir4(CO)11Br]− with the corresponding aromatic amine. In the solid state, cluster 2 has an approximate Cs symmetry with all terminal ligands as shown by an X-ray analysis. In solution, this unbridged structure is in dynamic equilibrium with two other isomeric forms having three edge-bridging CO’s on a common basal face and the amine ligand coordinated in axial or in radial position relative to this face. 相似文献
18.
Subsequent addition of 1,2-benzenedithiol (S2-H2) and nBuLi to a solution of [Ru(NO)Cl3 · xMeOH] in THF afforded exclusively the monomeric species NBu4[RuII(NO)(S2)2] (1). Formation of dimeric (NBu4)2[RuII(NO)(S2)2]2 (2) has been confirmed when the deprotonated ligand S2-Li2 was added to [Ru(NO)Cl3 · xMeOH] and allowed to stir for 30 h. The monomer 1 undergoes aerial oxidation to give (NBu4)2[RuIV(S2)3] (3). The reaction between RuCl3 · xH2O and S2-H2 in the presence of NaOMe, afforded the dinulear RuIII species (NMe4)2[RuIII(S2)2]2 (4). A modified method for the preparation of 1 is being employed to synthesize the osmium analogue NBu4[Os(NO)(S2)2] (5) effectively. The solid state structures of 1, 2 and 3 were determined by X-ray crystal structure analysis. A comparison of relevant bond distance data suggests that 1,2-benzenedithiolate acts as an “innocent” ligand. 相似文献
19.
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
20.
The preparation, crystal structures and magnetic properties of three copper(II) compounds of formulae [Cu2(dmphen)2(dca)4] (1), [Cu(dmphen)(dca)(NO3)]n (2) and [Cu(4,4′-dmbpy)(H2O)(dca)2] (3) (dmphen=2,9-dimethyl-1,10-phenanthroline, dca=dicyanamide and 4,4′-dmbpy=4,4′-dimethyl-2,2′-bipyridine) are reported. The structure of 1 consists of discrete copper(II) dinuclear units with double end-to-end dca bridges whereas that of 2 is made up of neutral uniform copper(II) chains with a single symmetrical end-to-end dca bridge. Each copper atom in 1 and 2 is in a distorted square pyramidal environment: two (1) or one (2) nitrile-nitrogen atoms from bridging dca groups, one of the nitrogen atoms of the dmphen molecule (1 and 2) and either one nitrile-nitrogen from a terminal dca ligand (1) or a nitrate-oxygen atom (2) build the equatorial plane whereas the second nitrogen atom of the heterocyclic dmphen fills the axial position (1 and 2). The copper-copper separations through double (1) and single (2) end-to-end dca bridges are 7.1337(7) (1) and 7.6617(7) (2). Compound 3 is a mononuclear copper(II) complex whose structure contains two neutral and crystallographically independent [Cu(4,4′-dmbpy)(H2O)(dca)2] molecules which are packed in two different layer arrangements running parallel to the bc-plane and alternating along the a-axis. The copper atoms in both molecules have slightly distorted square pyramidal surroundings with the two nitrogen atoms of the 4,4′-dmbpy ligand and two dca nitrile-nitrogen atoms in the basal plane and a water oxygen in the apical position. A semi co-ordinated dca nitrile-nitrogen from a neighbour unit [2.952(6) Å for Cu(2)-N] is in trans position to the apical water molecule in one of the two molecules, this feature representing part of the difference in supramolecular connections in the alternating layers referred to above. Magnetic susceptibility measurements for 1-3 in the temperature range 1.9-290 K reveal the occurrence of weak antiferromagnetic interactions through double [J=−3.3 cm−1 (1), ] and single [J=−0.57 cm−1 (2), ] dca bridges and across intermolecular contacts [θ=−0.07 K (3)]. 相似文献