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1.
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
2.
Gordana P. Vasi? Ivana D. Radojevi? Ljiljana R. ?omi? Sre?ko R. Trifunovi? 《Inorganica chimica acta》2010,363(13):3606-3610
Three new ligands and their palladium(II) complexes of general formula [PdCl2(R2-S,S-eddp)] (R = n-propyl, n-butyl and n-pentyl) have been synthesized and characterized by microanalysis, infrared and 1H and 13C NMR spectroscopy. Antimicrobial activity of these ligands and complexes was tested by microdilution method and both minimal inhibitory and microbicidal concentration were determined. These tested complexes demonstrated the significant antifungal activity against pathogenic fungi Aspergillus flavus and Aspergillus fumigatus. On the other hand, these complexes demonstrated moderate antibacterial activity. 相似文献
3.
The tris(pyrazolyl)amine ligands: tris[2-(1-pyrazolyl)methyl]amine (tpma), tris [3,5-dimethyl-1-pyrazolyl)methyl]amine (tdma), tris[2-(1-pyrazolyl)ethyl]amine (tpea), tris[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine (tdea) and bis(pyrazolyl)amine ligands: bis[2-(1-pyrazolyl)ethyl]amine (bpea) and bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine (bdea) react with [RhCl(cod)]2 in presence of NaBF4 (tpma, tdma and bdea) or AgBF4 (tpea, tdea and bpea) to lead to [Rh(cod)L] (BF4) (L=tpma (1), tdma (2), bdea (3), tpea (4), tdea (5) and bpea (6)). These complexes have been characterised by elemental analyses, conductivity, IR, 1H and 13C NMR spectroscopy and liquid mass (with electrospray) spectrometry. The 1H NMR spectra of 1, 2 show the presence of two isomers in solution in a 3:1 ratio (coordination κ2 or κ3 type) in a thermodynamic equilibrium. The steric bulk of cyclo-octa-1,5-diene causes it to prefer the κ2 mode of bonding as majority. Similar to previous published results, complexes 4 and 5 exist in a sole form in solution (probably κ2 isomer). Finally, the complexes 3 and 6 are fluxional. A NMR study shows that this fluxional process is not frozen at 183 K. 相似文献
4.
Malai Haniti S.A. Hamid Aminul Huq Mirza Boujemaa Moubaraki 《Inorganica chimica acta》2009,362(10):3648-41
New copper(II) complexes of general empirical formula, [Cu(NNS)X] (NNS = anionic forms of the 2-acetylpyrazine Schiff bases of S-methyl- and S-benzyldithiocarbazate, Hapsme and Hapsbz) and X = Cl−, Br−, NCS− and NO3− have been synthesized and characterized. X-ray crystal structures of the free ligand, Hapsbz and the complexes, [Cu(apsbz)(NO3)]∞, [Cu(apsme)(NCS)]2 and [Cu(apsme)Cl]2 have been determined. In the solid state, the Schiff base, Hapsbz remains in its thione tautomeric form with the thione sulfur atom trans to the azomethine nitrogen atom. X-ray diffraction shows that the [Cu(apsbz)(NO3)]∞ complex is a novel coordination polymer in which one of the nitrogen atoms of the pyrazine ring bridges two adjacent copper(II) ions. The Schiff base is coordinated to the copper(II) ion in its iminothiolate form via the thiolate sulfur atom, the azomethine nitrogen atom and one of the pyrazine nitrogen atoms, the overall geometry of each copper atom in the polymer being close to a square-pyramid. The complexes, [Cu(apsme)X]2 (X = NCS−, Cl−) are dimers in which each copper atom adopts a five-coordinate near square-pyramidal geometry with an N3S2 coordination environment. The Schiff base coordinates as a uninegatively charged tridentate ligand chelating via the pyridine and azomethine nitrogen atoms and the thiolate sulfur atoms. A nitrogen atom of a unidentate thiocayanate or chloride ligand and a bridging sulfur atom from a second ligand completes the coordination sphere. Room temperature μeff values for the complexes in the solid state are in the range 1.70-2.0 μB typical of uncoupled or weakly coupled Cu(II) centres. Variable temperature susceptibility studies show that the chain complex displays weak ferromagnetic coupling across the pyrazine bridges, while the S-bridged dinuclear compounds display either weak ferromagnetic or weak antiferromagnetic coupling that relates to subtle bridging geometry differences. EPR studies of frozen DMF solutions give rather similar g and ACu values for all compounds indicative of Cu(dx2-y2) ground state orbitals on the Cu centers. 相似文献
5.
Two isomers (R,S,R,S- and R,R,S,S-) of five coordinate complex [Cu(L)Cl]+ have been separated and characterised. These two isomers have significantly different spectrochemical and electrochemical properties. Absorption maximum of R,S,R,S-[Cu(L)Cl]+ shifts to longer wavelength and its reduction potential shifts to more positive direction comparing those of R,R,S,S-[Cu(L)Cl]+. R,S,R,S-[Cu(L)Cl]+ is significantly distorted to trigonal-bipyramidal structure, whereas R,R,S,S-[Cu(L)Cl]+ retains almost square-planar geometry. The average bond distance of Cu-N in basal plane of R,S,R,S-[Cu(L)Cl]+ is longer by 0.024 Å than that of R,R,S,S-[Cu(L)Cl]+, whereas the bond distance of Cu-Cl in former is shorter by 0.200 Å than that in latter. The isolated square-planar complexes of R,R,S,S- and R,S,R,S-[Cu(L)](ClO4)2 are converted to the R,R,S,S- and R,S,R,S-[Cu(L)Cl]+ by the addition of Cl− in nitromethane solution with the rate constants, k=1.70 (±0.02) and 8.31 (±0.07) M−1 s−1, respectively. 相似文献
6.
Reaction of the N-alkylaminopyrazole (NN′N) ligands bis[(3,5-dimethyl-1-pyrazolyl)methyl]ethylamine (bdmae) and bis[(3,5-dimethyl-1-pyrazolyl)methyl]isopropylamine (bdmai) with [PdCl2(CH3CN)2] in a 1:1 M/L ratio in CH2Cl2 produces cis-[PdCl2(NN′N)] (NN′N = bdmae (1), bdmai (2)). The solid state structure of complex 1 was determined by X-ray diffraction studies. The bdmae ligand is coordinated through the two Npz atoms to the metal atom, which completes its coordination with two chlorine atoms in a cis disposition.Treatment of the corresponding ligand with [PdCl2(CH3CN)2] in 1:1 M/L ratio in the presence of AgBF4 and metathesis with NaBPh4 in CH2Cl2/CH3OH (3:1) gave [PdCl(bdmae)](BPh4) (3), and in the presence of NaBPh4 in CH2Cl2/CH3CN (3:1) gave [PdCl(bdmai)](BPh4) (4). Complexes 1 and 2 were again obtained when complexes 3 and 4 were heated under reflux in a solution of Et4NCl in acetonitrile. These Pd(II) compounds were characterised by elemental analyses, conductivity measurements, IR, 1H and 13C{1H} NMR, HMQC and NOESY spectroscopies. The NMR studies of the complexes prove the rigid conformation of the ligands when they are complexed. 相似文献
7.
In situ cyanide bis-axial coordination of a square planar complex [CoIIIN2S2]−, containing a di-N-carboxamido and dithiolato tetradentate ligand, generates the highly nucleophilic species [CoIIIN2S2(CN)2]3−. Its di-S-chloromethylation and di-S-oxygenation products were isolated and structurally characterized. 相似文献
8.
Felix D. Sokolov Valery G. Shtyrlin Vasily V. Brusko Sergey V. Baranov Tadeusz Glowiak 《Inorganica chimica acta》2006,359(7):2087-2096
Thiourea, PhNHC(S)NHP(O)(OPri)2 (LH) chelates of CoII, NiII, and PdII ions have been obtained and investigated by single-crystal X-ray diffraction, UV, IR, NMR spectroscopy, and EI mass-spectrometry. The unusual 1,3-N,S-coordination via sulfur and NP(O) nitrogen atoms has been found in the trans-square-planar NiL2 and PdL2 complexes, whereas the 1,5-O,S-coordination is realized in the tetrahedral CoL2 complex. DFT calculations have revealed significant stabilization of the 1,3-N,S-structures due to stronger crystal field and the NH-OP hydrogen bonds. 相似文献
9.
Daniel Totev Daniel Carmona Luis A Oro Isabel T Dobrinovitch 《Inorganica chimica acta》2004,357(10):2889-2898
The synthesis of arene-ruthenium(II) and C5Me5-rhodium(III) and -iridium(III) complexes of chiral arene-chromium-tricarbonyl-based P∧P and P∧N ligands is described. Three complexes were characterized in the solid state by X-ray structural analysis. The complexes were tested in the catalytic hydrogen transfer reactions as well as in the kinetic resolution of racemic alcohols, where some complexes showed good conversion, but low enantioselectivity. 相似文献
10.
Ulrich Jürgen Scheele 《Inorganica chimica acta》2006,359(15):4891-4900
A series of six 3,6-bis(imidazolium-3-yl)pyridazine derivatives with different imidazole-N substituents have been synthesized and isolated as the salts [H2L]Cl2 (1a)-(6a) and [H2L](PF6)2 (1b)-(6b). Solid state structures have been determined crystallographically for eleven out of the twelve compounds, revealing diverse hydrogen bonding patterns that involve the imidazolium-C2H units and the anions. N-heterocyclic carbene (NHC) mercury(II) complexes [Hg2L2](PF6)4 (7)-(9) are readily formed in good yields from ligand precursors [H2L](PF6)2 and Hg(OAc)2, as long as imidazole-N substituents are not too bulky. X-ray crystallography reveals double helical bimetallic arrangements for the stable [Hg2L2]4+ cations. Ligand scrambling in [Hg2L2]4+ occurs only in the presence of free carbene precursor, presumably via an associative mechanism. 相似文献
11.
Pulakesh Bera 《Inorganica chimica acta》2009,362(8):2603-4433
Lead(II) complexes of S-methyldithiocarbazate (SMDTC), [Pb(SMDTC)(NO3)2] (1) and S-benzyldithiocarbazate (SBDTC), [Pb(SBDTC)(NO3)2] (2) have been synthesized for the first time and characterized by elemental analysis, IR and TGA techniques. The complexes were obtained by addition of the appropriate ligand to an aqueous ethanolic solution of lead(II) nitrate in 1:1 molar ratio. The X-ray crystal structure of complex 1 has been determined by single crystal X-ray diffractometry. In complex 1, lead(II) is in a nine coordinated sphere with seven oxygen atoms of the nitrate groups and thione sulfur, β-nitrogen of neutral bidentate NS chelating ligand. Three nitrate groups act as bidentate chelating whereas the fourth nitrate group is coordinating to the central lead(II) and at the same time it bridges with neighboring lead(II) atom. Coordination geometry of the central lead(II) atom has a tricapped trigonal prismatic arrangement with streochemically inactive lone pair. The lead atoms are linked into polymeric chains and these chains form twin polymeric ribbons linked through bridging oxygen atoms. The N-H?O hydrogen bond network between NSMDTC and Onitrate atom leads to self-assembled molecular conformation and stabilizes the crystal structure. The complex 2 with similar spectral and thermal behavior is expected to have a tricapped trigonal prismatic structure. The thermal behavior studies shows that the complexes start to decompose at relatively low temperature (ca. 110 °C) to give PbS residue. 相似文献
12.
The dinuclear V(V) complexes (VOL)2O (L = SAE (1), SAMP (2), SAP (3)) have been synthesized from VO(acac)2 and the corresponding tridentate ligands LH2 in methanol under reflux conditions and subsequent air oxidation in organic solvent. They have been characterized by IR and NMR spectroscopy, by thermogravimetric analysis, and by single crystal X-ray diffraction for 1 and 2. DFT calculations were carried out for a better understanding of the vibrational pattern, principally the V-O related vibrations. Complex [VO(SAP)]2O (3) catalyzes the epoxidation of cyclooctene by TBHP in water in the absence of any added solvent with good selectivity. 相似文献
13.
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
14.
The new N,N,O heteroscorpionate ligand 3,3-bis(1-vinylimidazol-2-yl)propionic acid (Hbvip) (5) was synthesised in five steps starting from 1-vinylimidazole. This ligand is closely related to 3,3-bis(1-methylimidazol-2-yl)propionic acid (Hbmip), but contains two vinyl linker groups which can be used for radical-induced polymerisation reactions. The κ3-N,N,O coordination behaviour of 5 was proven by the synthesis of the tricarbonyl complexes [Re(bvip)(CO)3] (6), [Mn(bvip)(CO)3] (7) and [Cu(bvip)2] (8). To obtain good yields of 6, it was synthesised in water instead of THF. The ligand as well as all three complexes were characterised by X-ray crystallography. Copolymerisation of 5 with pure methyl methacrylate (MMA) or a combination of MMA and ethylene glycol dimethacrylate (EGDMA) led to the solid phases P1 and P2. Polymer-bound rhenium and manganese tricarbonyl complexes could be obtained by the reaction of deprotonated P1 with [MBr(CO)5] (M = Re, Mn) and also by copolymerisation of 6 and 7 with MMA. In both cases, the facial tripodal binding behaviour was evidenced by IR spectra of the polymers. Furthermore, the content of metal incorporated in the polymers was determined by elemental analysis, AAS or ICP-OES measurements. Reaction of the deprotonated solid phase P1 with copper(II) chloride led to a blue solid-phase (P1-Cu). The UV-Vis absorption maximum of P1-Cu is found at 615 nm, which is almost identical to that found for 8. Thereby, it seems likely that P1 is flexible enough to form bisligand complexes with copper(II). This means that the copper centres act as a kind of crosslinking agents. In contrast, the heterogeneous reaction of P2 with copper(II) chloride yielded a lime green solid phase (P2-Cu). The bathochromic shift of the absorption maximum by 102 nm suggests one-sided bound copper centres. 相似文献
15.
Hendrikus F. Haarman Jan-Willem F. Kaagman Wilberth J.J. Smeets Anthony L. Spek Kees Vrieze 《Inorganica chimica acta》1998,270(1-2):34-45
The new rhodium(I) phenoxide complexes [Rh(OPh) (2,6-(CH=R2)2C5H3N)] (R2 = i-Pr(3), t-Bu(4)) containing strongly electrondonating N-N′-N ligands, have been prepared by a metathesis reaction of [RhCl(2,6-(CH=R2)2C5H3N)] (R2 = i-Pr (1), t-Bu (2)) with NaOPh. These rhodium(I) phenoxide complexes 3 and 4, which are very sensitive to O2 but stable towards H2O, give with phenol the adducts [Rh(OPh) (2,6-(CH=NR2)2C5H3N)] · HOPh (R2 = i-Pr (5), t-Bu (6)), which contain strong O-HO hydrogen bonds. The hydrogen bonded phenol could not be extracted with diethyl ether, while no exchange of the hydrogen bonded phenol and the phenoxide ligand in 4 is observed on the NMR time scale. However, a small excess of phenol results in exchange of the hydrogen bonded phenol, the coordinated phenoxide ligand and free phenol on the NMR time scale. Reaction of 3 and 4 with p-nitrophenol afforded [Rh(OC6H4-(NO2-4))(2,6-(CH=R2)2C5H3N)] · HOPh (R2 = i-Pr (7), t-Bu (8)) in which the formed phenol is hydrogen bonded to the Rh(I)-OC6H4-(NO2-4) moiety. The O-HO bond is less strong than in 5 and 6, as the hydrogen bonded phenol could be removed by diethyl ether.Treatment of 3 with acetyl chloride and benzoyl chloride in benzene at room temperature gave phenylacetate and RhCl2(C(O)C6H3) (2,6(C(H)=N-i-Pr)2C5H3N)] (15), and phenylbenzoate and [RhCl2(C(O)Ph) (2,6-(C(H)=N-i-Pr)2C5H3N)] (19), respectively. Complex 15 and the analogous complex [RhCl2(C(O)CH3) (2,6-(C(H)=N-t-Bu)2C5H3N)] (16) could also be prepared directly from acetyl chloride and 1 or 2, respectively. The single crystal X-ray determination of complex 16, monoclinic, space group P21/c, a = 10.0477(5), b= 11.7268(6), c= 19.2336(9) Å, β = 92.041(4)°, Z = 4, R1 = 0.0281, shows that the acetyl group occupies an axial position, while the N-N′-N ligand is positioned equatorially. In solution this geometry remains unchanged as was shown by variable temperature 1H NMR measurements. When the oxidative addition of acetyl chloride to 3 was carried out at −78°C in toluene the intermediate complex [RhCl(OPh) (C(O)Me) (2,6-(C(H)=N-i-Pr)2C5H3N)] (11) could be isolated, which at room temperature reductively eliminates phenylacetate with formation of 1. Oxidative addition of acetyl chlori de to 4 at room temperature gives [RhCl(OPh) (C(O)Me) (2,6-(C(H)=Nt-Bu)2C5H3N)] (12) which yields phenylacetate and 2 at 70°C in benzene by inductive elimination. Treatment of 3 with two equivalents of benzyl chloride afforded a mixture of [RhCl(OPh) (CH2Ph) (2,6-(C(H)=N-i-Pr)2C5H3N)] (13) and [RhCl2(CH2Ph) (2,6-(C(H)=N-i-Pr)2C5H3N)] (17) and some non-characterizable organic products, while 4 only yielded [RhCl(OPh) (CH2Ph) (2,6-(C(H)=N-tBu)2C5H3N)] (14). 相似文献
16.
《Inorganica chimica acta》2005,358(2):303-309
The reactions of two equivalents of the ligands POT or POZ with one equivalent of the rhodium complex [Rh(μ-Cl)(CO)2]2 afford the complexes [(POT)Rh(CO)Cl] (1) and [(POZ)Rh(CO)Cl] (2), respectively. The crystal structures of both complexes have been determined showing the rhodium centers to be into slightly distorted square planar environments. Preliminary screening of the catalytic systems POT/Rh and POZ/Rh in the asymmetric hydroformylation of styrene has been carried out. 相似文献
17.
A series of four mononuclear manganese (II) complexes with the N-tridentate neutral ligands 2,2′:6,2′′-terpyridine (terpy) and N,N-bis(2-pyridylmethyl)ethylamine (bpea) have been synthesized and crystallographically characterized. The complexes have five- to seven-coordinate manganese(II) ions depending on the additional ligands used. The [Mn(bpea)(Br)2] complex (1) has a five-coordinated manganese atom with a bipyramidal trigonal geometry, while [Mn(terpy)2](I)2 (2) is hexa-coordinated with a distorted octahedral geometry. Otherwise, the reactions of Mn(NO3)2 · 4H2O with terpy or bpea afforded novel seven-coordinate complexes [Mn(terpy)(NO3)2(H2O)] (3) and [Mn(bpea)(NO3)2] (4), respectively. 3 has a coordination polyhedron best described as a distorted pentagonal bipyramid geometry with one nitrate acting as a bidentate chelating ligand and the other nitrate as a monodentate one. 4 possesses a highly distorted polyhedron geometry with two bidentate chelating nitrate ligands. These complexes represent unusual examples of structurally characterized complexes with a coordination number seven for the Mn(II) ion and join a small family of nitrate complexes. 相似文献
18.
Mohammad Akbar Ali Aminul Huq Mirza Raymond J. Butcher Simon C. Drew Graeme R. Hanson Keith S. Murray 《Inorganica chimica acta》2005,358(13):3937-3948
New copper(II) complexes of general empirical formula, Cu(mpsme)X · xCH3COCH3 (mpsme = anionic form of the 6-methyl-2-formylpyridine Schiff base of S-methyldithiocarbazate; X = Cl, N3, NCS, NO3; x = 0, 0.5) have been synthesized and characterized by IR, electronic, EPR and susceptibility measurements. Room temperature μeff values for the complexes are in the range 1.75-2.1 μB typical of uncoupled or weakly coupled Cu(II) centres. The EPR spectra of the [Cu(mpsme)X] (X = Cl, N3, NO3, NCS) complexes reveal a tetragonally distorted coordination sphere around the mononuclear Cu(II) centre. We have exploited second derivative EPR spectra in conjunction with Fourier filtering (sine bell and Hamming functions) to extract all of the nitrogen hyperfine coupling matrices. While the X-ray crystallography of [Cu(mpsme)NCS] reveals a linear polymer in which the thiocyanate anion bridges the two copper(II) ions, the EPR spectra in solution are typical of a magnetically isolated monomeric Cu(II) centres indicating dissociation of the polymeric chain in solution. The structures of the free ligand, Hmpsme and the {[Cu(mpsme)NO3] · 0.5CH3COCH3}2 and [Cu(mpsme)NCS]n complexes have been determined by X-ray diffraction. The {[Cu(mpsme)NO3] 0.5CH3COCH3}2 complex is a centrosymmetric dimer in which each copper atom adopts a five-coordinate distorted square-pyramidal geometry with an N2OS2 coordination environment, the Schiff base coordinating as a uninegatively charged tridentate ligand chelating through the pyridine and azomethine nitrogen atoms and the thiolate, an oxygen atom of a unidentate nitrato ligand and a bridging sulfur atom from the second ligand completing the coordination sphere. The [Cu(mpsme)(NCS)]n complex has a novel staircase-like one dimensional polymeric structure in which the NCS− ligands bridge two adjacent copper(II) ions asymmetrically in an end-to-end fashion providing its nitrogen atom to one copper and the sulfur atom to the other. 相似文献
19.
《Inorganica chimica acta》2004,357(10):2818-2826
[{Rh(cod)Cl}2] (cod=1,5-cyclooctadiene) reacts with o-(diphenylphosphino)benzaldehyde (PPh2(o-C6H4CHO)) (Rh:P=1:1) in the presence of aromatic diamines or 8-aminoquinoline (NN) to give acylhydride [Rh(Cl)(H){PPh2(o-C6H4CO)}(NN)] species. The oxidative addition of PPh2(o-C6H4CHO) in the presence of (NN) and PPh3 gives cationic species [Rh(H){PPh2(o-C6H4CO)} (PPh3)(NN)]+ containing mutually trans phosphorus atoms. When (NN)=8-aminoquinoline, a mixture of two isomers is obtained. These isomers differ in the nitrogen cis to the hydride, amino or quinolinic. By using Rh:PPh2(o-C6H4CHO)=1:2 stoichiometric ratios, oxidative addition of one PPh2(o-C6H4CHO) and P-coordination of another PPh2(o-C6H4CHO) occurs. The aldehyde group undergoes then a condensation reaction with the coordinated amine to afford new PNN terdentate ligands, phosphine-amino-imine when (NN)=diamine or phosphine-diimine when (NN)=8-aminoquinoline. These reactions give selectively the corresponding complexes [Rh(H){PPh2(o-C6H4CO)}(PNN)]+ containing trans phosphorus atoms and the hydride cis to the new imino group. X-ray diffraction studies of the PNN complexes are reported. 相似文献
20.
Two new 3,5-dimethylpyrazolic derived ligands that are N1-substituted by diamine chains, 1-[2-(diethylamino)ethyl]-3,5-dimethylpyrazole (L1) and 1-[2-(dioctylamino)ethyl]-3,5-dimethylpyrazole (L2) were synthesised. Reaction of the ligands, L1 and L2, with [MCl2(CH3CN)2] yielded [MCl2(L)] (M = Pd(II), Pt(II)) complexes. These complexes were characterised by elemental analyses, conductivity measurements, IR, 1H, 13C{1H} and 195Pt{1H} NMR spectroscopies. The crystal structure of [PdCl2(L1)] was determined by single-crystal X-ray diffraction methods. The structure consists of mononuclear units. The Pd(II) atom is coordinated by a pyrazolic nitrogen, an amine nitrogen and two chlorine atoms in a cis disposition. In this structure, C-H?Cl, C-H?H-C and C-H?C-H intermolecular interactions have been identified. 相似文献