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1.
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
2.
The reactions of [PtMe3(OAc)(bpy)] (4) with the N,S and S,S containing heterocycles, pyrimidine-2-thione (pymtH), pyridine-2-thione (pytH), thiazoline-2-thione (tztH) and thiophene-2-thiol (tptH), resulted in the formation of the monomeric complexes [PtMe3(-κS)(bpy)] ( = pymt, 5; pyt, 6; tzt, 7; tpt, 8), where the heterocyclic ligand is coordinated via the exocyclic sulfur atom. In contrast, in the reactions of [PtMe3(OAc)(Me2CO)x] (3, x = 1 or 2) with pymtH, pytH, tztH and tptH dimeric complexes [{PtMe3(μ-)}2] (μ- = pymt, 9; pyt, 10; tzt, 11) and the tetrameric complex [{PtMe3(μ3-tpt-κS)}4] (12), respectively, were formed. The complexes were characterized by microanalyses, 1H and 13C NMR spectroscopy and negative ESI-MS (12) measurements. Single-crystal X-ray diffraction analysis of [PtMe3(pymt-κS)(bpy)] (5) exhibited a conformation where the pymt ligand lies nearly perpendicular to the complex plane above the bpy ligand that was also confirmed by quantum chemical calculations on the DFT level of theory. 相似文献
3.
Yolanda Pérez Isabel Sierra Mariano Fajardo Isabel del Hierro 《Inorganica chimica acta》2007,360(2):607-618
In view of the wide applicability and versatility of titanium based Lewis acids in selective organic synthesis including asymmetric synthesis, we have synthesized a family of mono and polyatomic titanium derivatives. The polymetallic complexes prepared are bridged by pyridimine, quinone and triazine based ligands. The synthesis of [{Ti(O-i-Pr)3(Oddbf)}2] (1), [Ti(O-i-Pr)2(Oddbf)2] (2), [{Ti(O-i-Pr)2(Oddbf)(OMent)}2] (3) (ddbfO = 2,3-dihydro-2,2-dimethyl-benzofuranoxo; MentO = (1R,2S,5R)-(−)-menthoxo), [{Ti(O-i-Pr)3(OMenpy)}2] (4), [Ti(O-i-Pr)2(OMenpy)2] (5) (MenpyO = (1S,2S,5R)-(−)-menthoxo-pyridine); [{(Ti(OR)3)2L}n] (RO = isopropoxo, (1R,2S,5R)-(−)-menthoxo) (6-11) and [{(Ti(O-i-Pr)3)3L}n] (12) was accomplished from a Lewis acid such as Ti(O-i-Pr)4, [{Ti(O-i-Pr)3(OMent)}2] or [Ti(OMent)4] and chelating ligands (ddbfOH = 2,3-dihydro-2,2-dimethyl-benzofuranol; MenpyOH = (1R,2S,5R)-(−)-5-methyl-2-isopropyl-1-(2′-pyridinyl)cyclohexan-1-ol; LH2 = 4,6-dihydroxy-2,5-diphenyl-pyrimidine, 2,4-dihydroxy-5,6-dimethyl-pyrimidine, 5,8-dihydroxy-1,4-napthoquinone, 2,5-dihydroxy-1,4-benzoquinone and LH3 = cyanuric acid) that provide a rigid framework for the metal centre. The molecular structure of 5 has been determined by single crystal X-ray diffraction studies. 相似文献
4.
Roderick C. Jones Michael G. Gardiner Vicki-Anne Tolhurst 《Inorganica chimica acta》2010,363(1):77-295
Ligands containing the 2-organochalcogenomethylpyridine motif with substituents in the 4- or 6-position of the pyridyl ring, R4,R6-pyCH2ER1 [R4 = R6 = H, ER1 = SMe (1), SeMe (2), SPh (6), SePh (7); R4 = Me, R6 = H, ER1 = SMe (3), SPh (8), SePh (9); R4 = H, R6 = Me, ER1 = SMe (4), SPh (10), SePh (11); R4 = H, R6 = Ph, ER1 = SMe (5), SPh (12), SePh (13)] are obtained on the reaction of R4,R6-pyMe with LiBun followed by R1EER1. On reaction with PdCl2(NCMe)2, the ligands with a 6-phenyl substituent form cyclopalladated species PdCl{6-(o-C6H4)pyCH2ER1-C,N,E} (5a, 12a, 13a) with the structure of 13a (ER1 = SePh) confirmed by X-ray crystallography; other ligands form complexes of stoichiometry PdCl2(R4,R6-pyCH2ER1). Complexes with R6 = H are monomeric with N,E-bidentate configurations, confirmed by structural analysis for 3a (R4 = Me, ER1 = SMe), 7a (R4 = H, ER1 = SePh) and 9a (R4 = Me, ER1 = SePh). Two of the 6-methyl substituted complexes examined by X-ray crystallography are oligomeric with trans-PdCl2(N,E) motifs and bridging ligands, trimeric [PdCl2(μ-6-MepyCH2SPh-N,S)]3 (10a) and dimeric [PdCl2(μ-6-MepyCH2SePh-N,Se)]2 (11a). This behaviour is attributed to avoidance of the Me···Cl interaction that would occur in the cis-bidentate configuration if the pyridyl plane had the same orientation with respect to the coordination plane as observed for 3a, 7a and 9a [dihedral angles 8.0(2)-16.8(2)°]. When examined as precatalysts for the Mizoroki-Heck reaction of n-butyl acrylate with aryl halides in N,N-dimethylacetamide at 120 °C, the complexes exhibit the anticipated trends in yield (ArI > ArBr > ArCl, higher yield for electron withdrawing substituents in 4-RC6H4Br and 4-RC6H4Cl). The most active precatalysts are PdCl2(R4-pyCH2SMe-N,S) (R = H (1a), Me (3a)); complexes of the selenium containing ligands exhibit very low activity. For closely related ligands, the changes SMe to SPh, 6-H to 6-Me, and 6-H to 6-Ph lead to lower activity, consistent with involvement of both the pyridyl and chalcogen donors in reactions involving aryl bromides. The precatalyst PdCl2(pyCH2SMe-N,S) (1a) exhibits higher activity for the reaction of aryl chlorides in Bun4NCl at 120 °C as a solvent under non-aqueous ionic liquid (NAIL) conditions. 相似文献
5.
Reactions of [PtMe3(bpy)(Me2CO)][BF4] (2) with the thionucleobases 2-thiouracil (s2Ura), 4-thiouracil (s4Ura) and 2,4-dithiouracil (s2s4Ura) resulted in the formation of complexes of the type [PtMe3(bpy)(L-κS)][BF4] (L = s2Ura, 3; s4Ura, 4; s2s4Ura, 5). The complexes were characterized by NMR spectroscopy (1H, 13C, 195Pt), IR spectroscopy as well as microanalyses. The coordination through the C4S groups (4, 5) was additionally confirmed by DFT calculations, where it was shown that these complexes [PtMe3(bpy)(L-κS4)]+ (L = s4Ura, s2s4Ura) are about 5.8 (4b) and 3.3 kcal/mol (5b), respectively, more stable than the respective complexes, having thiouracil ligands bound through the C2X groups (X = O, 4a; S, 5a). For [PtMe3(bpy)(s2Ura-κS2)][BF4] (3) no preferred coordination mode could be assigned solely based on DFT calculations. Analysis of NMR spectra showed the κS2 coordination. In vitro cytotoxic studies of complexes 3−5 on nine different cell lines (8505C, A253, FaDu, A431, A549, A2780, DLD-1, HCT-8, HT-29) revealed in most cases moderate activities. However, 3 and 5 showed significant activity towards A549 and A2780, respectively, possessing IC50 values comparable to those of cisplatin. Cell cycle perturbations and trypan blue exclusion test on cancer cell line A431 using [PtMe3(bpy)(s2s4Ura-κS4)][BF4] (5) showed induction of apoptotic cell death. Furthermore, the reaction of [PtMe3(OAc-κ2O,O′)(Me2CO)] (6) with 4-thiouracil yielded the dinuclear complex [(PtMe3)2(μ-s4Ura-H)2] (7), which has been characterized by microanalysis, NMR (1H, 13C, 195Pt) and IR spectroscopy as well as ESI mass spectrometry. X-ray diffraction analysis of crystals yielded in an isolated case exhibited the presence of a hexanuclear thiouracilato platinum(IV) complex, possessing each three different kinds of methyl platinum(IV) moieties and 4-thiouracilato ligands. This exhibited the ability of 4-thiouracil platinum(IV) complexes to form multinuclear complexes. 相似文献
6.
Mai Kotera 《Inorganica chimica acta》2008,361(5):1479-1484
The crystal structures of mononuclear (azido)(pentamethylcyclopentadienyl)iridium(III) complexes bearing 2- or 8-quinolinethiolate (n-Sqn−), [Cp∗Ir(N3)(n-Sqn)] {n = 2 (1) or 8 (2); Cp∗ = η5-C5Me5} have been determined by X-ray analysis. The 2-Sqn complex, 1, acquires severe steric strains in the four-membered κ2N,S chelate ring, while the 8-Sqn isomer, 2, forms a strain-free five-membered planar κ2N,S chelate ring. It has also been revealed that the corresponding benzimidazole-2-thiolate (Hbimt−) complex, which was obtained similarly to the above n-Sqn complexes from [Cp∗Ir(N3)2]2 and Na(Hbimt), takes an unsymmetrical dinuclear structure bridged by two Hbimt− ligands with different bonding modes, [Cp∗Ir(N3){μ(S:N1)-Hbimt}{μ(S:S)-Hbimt}Ir(N3)Cp∗] · MeOH (3). 相似文献
7.
One monomeric neutral Cu(II) complex [(pmtpm)CuCl2] (1) is reported by Lindoy and Livingstone [8]. Two new complexes namely, μ-Cl bridged binuclear Cu(II) complex [{(pmtpm)Cu(Cl)}2 μ-Cl](ClO4) (2) and a bis μ-Cl bridged binuclear Cu(II) complex [{(pmtpm)Cu}2(μ-Cl)2](ClO4)2 (3) derived from a tridentate Schiff base ligand, 2-pyridyl-N-(2′-methylthiophenyl)methyleneimine (pmtpm) were synthesized and characterized by various spectroscopic methods and by X-ray crystallography. (N2S)CuCl2 chromophore(s) of distorted square pyramidal coordination geometries around Cu(II) ion(s) have been observed for all the complexes 1-3. The equatorial sites of the square plane comprise two N and a thioether S donor atoms of the pmtpm ligand as well as one Cl− ion (terminal in 1 and 2, and bridging in 3) while the remaining axial site is occupied by a terminal Cl− ion (for 1) or a bridging Cl− ion (for 2 and 3). The equatorial Cu-Cl distances are much shorter [1: 2.2511(4) Å, 2: 2.2307(12) Å, 3: 2.2513(12) Å] than the axial Cu-Cl distances [1: 2.4394(4) Å, 2: 2.5597(9) Å, 3: 2.7037(12) Å]. The correlation of an axial Cu-Cl bond elongation with a lower g|| value in the solid state EPR spectrum and a blue shifted ligand field transition in the solid and solution phase absorption spectrum has been observed. 相似文献
8.
A series of dinuclear copper(II) complexes involving 6-(benzylamino)purine derivatives, (HLn), as bridging ligands were synthesized, characterized and tested for both their in vitro and in vivo antioxidant activities. Based on results of elemental analyses, temperature dependence of magnetic susceptibility measurements, UV-vis, FTIR, EPR, NMR and MALDI-TOF mass spectroscopy, conductivity measurements and thermal analyses, the complexes with general compositions of [Cu2(μ-HLn)4Cl2]Cl2 · 2H2O (1-4) and [Cu2(μ-HLn)2(μ-Cl)2Cl2] (5-7) were prepared {where n = 1-4; HL1 = 6-[(2-methoxybenzyl)amino]purine, HL2 = 6-[(4-methoxybenzyl)amino]purine, HL3 = 6-[(2,3-dimethoxybenzyl)amino]purine and HL4 = 6-[(3,4-dimethoxybenzyl)amino]purine}. In the case of complexes 2, 3, 5 and 7, the antioxidant activities were studied by both in vitro {superoxide dismutase-mimic (SOD-mimic) activity} and in vivo {cytoprotective effect against the alloxan-induced diabetes (antidiabetic activity)} methods. The obtained IC50 value of the SOD-mimic activity for the complex 5 (IC50 = 0.253 μM) was shown to be even better than that of the native bovine Cu,Zn-SOD enzyme (IC50 = 0.480 μM), used as a standard. As for the antidiabetic activity, the pretreatment of mice with complexes 3 and 7 led to the complete elimination of cytotoxic attack of alloxan and its free radical metabolites, used as a diabetogenic agent. The cytoprotective effect of these compounds was proved by the preservation of the initial blood glucose levels of the pretreated animals, as against the untreated control group. 相似文献
9.
Two complexes of the formula [MH3L](ClO4)2 [M = Cu(II) (1), Ni(II) (2)] have been prepared by the reaction of M(ClO4)2 · 6H2O with the ligand (H3L) formed by the Schiff base condensation of tris(2-aminoethyl)amine (tren) with three molar equivalents of 4-methyl-5-imidazolecarboxaldehyde and structurally and magnetically characterized. The structures of 1 and 2 are isomorphous with each other and with the iron(II) complex of H3L which has been reported previously. The ligand, while potentially heptadentate, forms six coordinate complexes with both metal centers forming three M-Nimine and three M-Nimidazole bonds. The tren central N atom is at a nonbonded distance from M of 3.261 Å for 1 and 3.329 Å for 2. The neutral complex CuHL 3 was prepared by reaction of H3L with Cu(OCH3)2 and the ionic complex Na[NiL] 4 was prepared by deprotonation of 2 with aqueous sodium hydroxide. Magnetic measurements of 1-3 are consistent with the spin-only values expected for S = 1/2 (d9, Cu(II)) and S = 1 (d8, Ni (II)) systems. 相似文献
10.
Rebecca A. Swanson Joseph B. Gibbons Brian O. Patrick Arnold L. Rheingold 《Inorganica chimica acta》2011,368(1):74-83
The reaction of Pt(COD)Cl2, where COD is 1,5-cyclooctadiene, with one equivalent of a diamidato-bis(phosphino) Trost ligand ((R,R)-2 = N,N′-bis(2-diphenylphosphino-1-benzoyl)-(1R,2R)-1,2-diaminocyclohexane, (R,R)-3 = N,N′-bis(2-diphenylphosphino-1-naphthoyl)-(1R,2R)-1,2-diaminocyclohexane, or (±)-4 = N,N′-bis(2-diphenylphosphino-1-benzoyl)-1,2-bis(aminobenzene)) in the presence of base afforded square planar diamidato-bis(phosphino) platinum(II) complexes (R,R)-2-Pt, (R,R)-3-Pt, (±)-4-Pt. Characterization of all complexes included the solution and solid state structure determination of each complex based on multinuclear NMR and X-ray analyses, respectively. Stability of the complexes in acid was examined on addition of HCl to (R,R)-2-Pt in chloroform and compared to the unreactive nature of the similar diamidato-bis(phosphino) complex 1-Pt (1 = 1,2-bis-N-[2′-(diphenylphosphino)benzoyl]diamino-benzene) in the presence of acid. Protonation of the bound amidato nitrogen atoms of (R,R)-2-Pt was observed along with decoordination of the nitrogen atoms from the platinum(II) center producing (R,R)-2-PtCl2 in quantitative yield by NMR analysis. Confirmation of the product was made on comparison of the NMR spectra to that of authentic (R,R)-2-PtCl2 prepared on reaction of Pt(COD)Cl2 with (R,R)-2 in CH2Cl2 and characterized by single-crystal X-ray diffraction analysis and NMR spectroscopy. Results add to the knowledge of rich coordination chemistry of bis(phosphino) ligands with late transition metals, metal-amidato chemistry, and has implications in catalysis. 相似文献
11.
Laura Battan Mario Manassero Alessandro Pasini Mirella Sansoni 《Inorganica chimica acta》2005,358(3):555-564
The interaction of an excess of the title ligands L− with the cis-Pt(phos)2 moieties gives compounds a-bcis-[Pt(L-O)2(phos)2] (a, phos = P(Ph)3; b, phos = 1/2 dppe), in which O- is preferred to S-coordination. Such preference is confirmed by the fact that the same products are obtained by reaction of excess of L− with the previously reported a-d complexes [Pt(L-O,S)(phos)2]+, (c, phos = PPh3, d, phos = 1/2 dppe), for which chelate ring opening occurs with rupture of Pt-S rather than Pt-O bonds. Compound a can be obtained also by oxidative addition of HL to [Pt(PPh3)3]. The Pt-O bonds in compounds a-d are stable towards substitution by Me2SO, pyridine and tetramethylthiourea. Substitution of L’s occurs with N,N′-diethyldithiocarbamate, which forms a very stable chelate with Pt(II). Thiourea and N,N′-dimethylthiourea also react, because they give rise to cyclometallated products [Pt(phos)2(NRC(S)NHR)]+ (R = H, CH3), with one ionised thioamido group, as revealed by an X-ray investigation of [Pt(PPh3)2(NHC(S)NH2)]+. The preference of O versus S coordination, as well as the stability of the Pt-O bonds, are discussed in terms of antisymbiosis. 相似文献
12.
Marion Graf 《Inorganica chimica acta》2011,371(1):42-43
The synthesis of bis-cyclometalated aminocarboxylato complexes [M(α-aminocarboxylato)(ptpy)2] (M = Rh, 3, 4, 5; M = Ir, 6, 7, 8), ptpy = 2-(p-tolyl)pyridinato; aminocarboxylato = glycinato, l-alaninato, l-prolinato) from [{M(μ-Cl)(ptpy)2}2] (M = Rh, 1; M = Ir, 2) is described. The molecular structure of [Ir(l-alaninato)(ptpy)2] (7) was confirmed by a single-crystal X-ray diffraction study. Compound 7 crystallized from methanol-iso-hexane in the space group P21. For 7 the two diastereoisomers ΔIr, SC and ΛIr, SC were found crystallizing twice per unit. Absorption and emission spectra were recorded. The rhodium compounds are weak yellow-green and the iridium species strong green emitters. 相似文献
13.
Mitsushiro Nomura 《Inorganica chimica acta》2004,357(8):2294-2300
The electrochemical behavior of the S,S′-bridged adducts of square planar metalladithiolene complexes was investigated by using cyclic voltammetry and electrochemical spectroscopies (visible, near-IR, and ESR). The norbornene-bridged S,S′-adduct [Ni(S2C2Ph2)2(C7H8)] (2a; C7H8=norbornene) formed by [Ni(S2C2Ph2)2] (1a) and quadricyclane (Q) was dissociated by an electrochemical reduction, and anion 1a− and norbornadiene (NBD) were formed. Q was isomerized to NBD in the overall reaction. The o-xylyl-bridged S,S′-adduct [Ni(S2C2Ph2)2(CH2)2(C6H4)] (3a; (CH2)2(C6H4)=o-xylyl) was also dissociated by an electrochemical reduction, and this reaction gave the o-xylyl radical (o-quinodimethane). The reduction of complex 3a in the presence of excess o-xylylene dibromide underwent the catalytic formation of o-quinodimethane. The butylene-bridged S,S′-adduct [Ni(S2C2Ph2)2(CH2)4] (4a; (CH2)4=butylene) was stable on an electrochemical reduction. The lifetimes of reduced species of these adducts 2a-4a were influenced by the stability of the eliminated group (stability: NBD > o-xylyl radical (o-quinodimethane) > butylene radical). Therefore, the reduced species are stable in the sequence 4a− > 3a− > 2a−. Although the palladium complex [Pd(S2C2Ph2)2] (1b) was easier to reduce than the nickel complex 1a or the platinum complex [Pt(S2C2Ph2)2] (1c), their S,S′-adducts were easier to reduce in the order of Ni adduct > Pd adduct > Pt adduct. 相似文献
14.
Reactions of 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L1), 2-(3,5-diphenylpyrazol-1-ylmethyl)pyridine (L2), 2-(3,5-di-tert-butylpyrazol-1-ylmethyl)pyridine (L3) and 2-(3-p-tolylpyrazol-1-ylmethyl)pyridine (L4) with K2[PtCl4] in a mixture of ethanol and water formed the dichloro platinum complexes [PtCl2(L1)] (1), [PtCl2(L2)] (2), [PtCl2(L3)] (3) and [PtCl2(L4)] (4). Complex 1, [PtCl2(L1)], could also be prepared in a mixture of acetone and water. Performing the reactions of L2 and L3 in a mixture of acetone and water, however, led to C-H activation of acetone under mild conditions to form the neutral acetonyl complexes [Pt(CH2COCH3)Cl(L2)] (2a) and [Pt(CH2COCH3)Cl(L3)] (3a). The same ligands reacted with HAuCl4 · 4H2O in a mixture of ethanol and water to form the gold salts [AuCl2(L1)][AuCl4] (5) [AuCl2(L2)][Cl] (6) [AuCl2(L3)][Cl] (7) and [AuCl2(L4)][AuCl4] (8); however, with the pyrazolyl unit in the para position of the pyridinyl ring in 4-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L5), 4-(3,5-diphenylpyrazol-1-ylmethyl)pyridine (L6) neutral gold complexes [AuCl3(L5)] (9) and [AuCl2(L6)] (10) were formed; signifying the role the position of the pyrazolyl group plays in product formation in the gold reactions. X-ray crystallographic structural determination of L6, 2, 33a, 8 and 10 were very important in confirming the structures of these compounds; particularly for 3a and 8 where the presence of the acetonyl group confirmed C-H activation and for 8 where the counter ion is . Cytotoxicity studies of L2, L4 and complexes 1-10 against HeLa cells showed the Au complexes were much less active than the Pt complexes. 相似文献
15.
The reaction of trans(N)-[Co(d-pen)2]− (pen = penicillaminate) with HgCl2 or HgBr2 in the molar ratios of 1:1 gave the sulfur-bridged heterodinuclear complex, [HgX(OH2){Co(d-pen)2}] (X = Cl (1a) or Br (1b)). A similar reaction in the ratio of 2:1 produced the trinuclear complex, [Hg{Co(d-pen)2}2] (1c). The enantiomers of 1a and 1c, [HgCl(OH2){Co(l-pen)2}] (1a′) and [Hg{Co(l-pen)2}2] (1c′), were also obtained by using trans(N)-[Co(l-pen)2]− instead of trans(N)-[Co(d-pen)2]−. Further, the reaction of cis · cis · cis-[Co(d-pen)(l-pen)]− with HgCl2 in the molar ratio of 1:1 resulted in the formation of [HgCl(OH2){Co(d-pen)(l-pen)}] (2a). During the formations of the above six complexes, 1a, 1b, 1c, 1a′, 1c′, and 2a, the octahedral Co(III) units retain their configurations. On the other hand, the reaction of cis · cis · cis-[Co(d-pen)(l-pen)]− with HgCl2 in the molar ratio of 2:1 gave not [Hg{Co(d-pen)(l-pen}2] but [Hg{Co(d-pen)2}{Co(l-pen)2}] (2c), accompanied by the ligand-exchange on the terminal Co(III) units. The X-ray crystal structural analyses show that the central Hg(II) atom in 1c takes a considerably distorted tetrahedral geometry, whereas that in 2c is of an ideal tetrahedron. The interconversion between the complexes is also examined. The electronic absorption, CD, and NMR spectral behavior of the complexes is discussed in relation to the crystal structures of 1c and 2c. 相似文献
16.
The reaction of 2-benzoylpyridine-N(4)-cyclohexylthiosemicarbazone [HBPCT, (1)] ligand with organotin(IV) chloride(s) lead to the formation of three new organotin(IV) complexes: [MeSnCl2(BPCT)] (2), [PhSnCl2(BPCT)] (3) and [Ph2SnCl(BPCT)] (4). The ligand (1) and its organotin(IV) complexes (2-4) have been synthesized and characterized by CHN analyses, molar conductivity, UV-Vis, FT-IR and 1H NMR spectral studies. The single crystal X-ray diffraction studies indicated that [PhSnCl2(BPCT)] (3) is six coordinated and adopts strongly a distorted octahedral configuration with the coordination through pyridine-N, azomethine-N and thiolato-S atoms of the ligand. The crystal system of [PhSnCl2(BPCT)] (3) is orthorhombic with space group P2ac2n and the unit cell dimensions: a = 28.1363(5) Å, b = 9.5970(2) Å, c = 9.4353(2) Å. 相似文献
17.
In search for new conglomerates, seven stereochemically labile complexes between MCl2 (M = Co, Cu, Ni, Zn) and bidentate ligands, the commercially available N,N,N′-trimethylethane-1,2-diamine (trimeda) and the somewhat bulkier N-isopropyl-N,N′,N′-trimethylethane-1,2-diamine (itmeda), have been synthesized and characterized using single crystal X-ray diffraction. The trimeda and itmeda ligands exhibit chirogenic nitrogen centers and may form chiral metal complexes that are candidates for total spontaneous resolution. Copper(II) chloride forms the dimeric meso complexes [{CuCl2(trimeda)}2] (1) and [{CuCl2(itmeda)}2] (2), while [CoCl2(trimeda)2] (3) and [NiCl2(trimeda)2] (4) exhibit six-coordinate but chiral (R,R)- and (S,S)-complexes. Three examples of the chiral target complex, comprising four-coordinate stereochemically labile monomers, was successfully prepared, viz. [NiCl2(itmeda)] (5), [ZnCl2(itmeda)] (6), and [CoCl2(itmeda)] (7).In all seven complexes, the λ-conformation of the five-membered trimeda-metal chelate ring corresponds to the (S)-configuration at nitrogen, and vice versa. Supramolecular interactions in 3 and 4 form hydrogen-bonded heterochiral ribbons. However, crystals of 5-7 display homochiral interactions resulting in polar phases. Weak CH-Cl interactions in 5 and 6 form homochiral layers. In 7, interactions form homochiral helices along the a-axis. 相似文献
18.
Damián Fernández 《Inorganica chimica acta》2005,358(9):2575-2584
The distorted square-planar complexes [Pd(PNHP)Cl]Cl (1) (PNHP = bis[2-(diphenylphosphino)ethyl]amine), [M(P3)Cl]Cl [P3 = bis[2-(diphenylphosphino)ethyl]phenylphosphine; M = Pd (2), Pt (3)] and [Pt(NP3)Cl]Cl (5) (NP3 = tris[2-(diphenylphosphino)ethyl]amine), coexisting in the later case with a square-pyramidal arrangement, react with one equivalent of CuCl to give the mononuclear heteroionic systems [M(L)Cl](CuCl2) [L = PNHP, M = Pd (1a); L = P3, M = Pd (2a), Pt (3a); L = NP3, M = Pt (5a)]. The crystal structure of 3a confirms that Pt(II) retains the distorted square-planar geometry of 3 in the cation with P3 acting as tridentate chelating ligand, the central P atom being trans to one chloride. The counter anion is a nearly linear dichlorocuprate(I) ion. However, the five-coordinate complexes [Pd(NP3)Cl]Cl (4), [M(PP3)Cl]Cl (M = Pd (6), Pt (7); PP3 = tris[2-(diphenylphosphino)ethyl] phosphine) containing three fused five-membered chelate rings undergo a ring-opening by interaction with one (4, 6, 7) and two (6, 7) equivalents of CuCl with formation of neutral MCu(L)Cl3 [L = NP3, M = Pd (4a); L = PP3, M = Pd (6a), Pt (7a)] and ionic [MCu(PP3)Cl2](CuCl2) [M = Pd (6b), Pt (7b)] compounds, respectively. The heteronuclear systems were shown by 31P NMR to have structures where the phosphines are acting as tridentate chelating ligands to M(II) and monodentate bridging to Cu(I). Further additions of CuCl to the neutral species 6a and 7a in a 1:1 ratio resulted in the achievement of the ionic complexes 6b and 7b with ions as counter anions. It was demonstrated that the formation of heterobimetallic or just mononuclear mixed salt complexes was clearly influenced by the polyphosphine arrangement with the tripodal ligands giving the former compounds. However, complexes [M(NP3)Cl]Cl constitute one exception and the type of reaction undergone versus CuCl is a function of the d8 metal centre. 相似文献
19.
Eight mononuclear complexes with multitopic C2-symmetry ligands, [Cu(L)]ClO4, [Mn(L)Cl(H2O)]PF6, (L=N,N′-bis[(S)-prolyl]phenylenediamine (1), N,N′-bis[(S)-N-benzylprolyl]phenylenediamine (2), N,N′-bis{[(S)-pyrrolidin-2-yl]methyl}phenylenediamine (3), N,N′-bis-{[(S)-N-benzyl-pyrrolidin-2-yl]methyl}phenylenediamine (4)) have been prepared and characterised by analytical (elemental analysis, and mass spectroscopy) and FT IR, NMR and electronic spectroscopies. The data show that the ligands are neutral and coordinate to the metal in a tetradentate manner. The N,N′-bis[(S)-prolyl]phenylenediamine ligand also appears as an anionic species, (LH-2), and the single crystal structure determination of the respective complex, [Cu(1)]H2O, is reported. This new family of Cu-complexes catalyse the cyclopropanation of styrene with ethyl and t-butyl diazoacetate to afford cis/trans 2-phenylcyclopropan-1-carboxylates with good yields and selectivity against dimerisation and low ee (<10%). On the other hand, the manganese and copper complexes also catalyse the oxidation of organic sulfides to sulfoxides with high selectivity, and moderate to low enantioselectivity. If an excess of oxidant were used the reaction yields sulfone as only product with excellent yield. 相似文献
20.
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