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1.
The [Pd(cod)(cotl)]ClO4 complex (cod = cycloocta-1,5-diene; cotl = cyclooctenyl, C18H13 ) undergoes substitutions with new Schiff base ligands containing benzimidazole L [L = 2-(2-N-n-propylidenephenyl)benzimidazole (L1); 2-(2-N-i-propylidenephenyl)benzimidazole (L2); 2-(2-N-n-butylidenephenyl)benzimidazole (L3); 2-(2-N-i-butylidenephenyl)benzimidazole (L4)]. Facile displacement of cod by L occurs to produce complexes of the type [Pd(cotl)L]ClO4· nMe2CO (n= 0; L = L1, L2 or L3; n= 2, L = L4). Dihalobridge complexes of the type [Pd(cotl)X]2(X = Cl or Br) undergo halogen-bridge cleavage with L1–L4 to give mononuclear complexes of the type Pd(cotl)LX · nH2O (n= 2, X = Cl, L = L1; n= 0, X = Br, L = L1; n= 0, X = Cl, L = L2; n= 0, X = Cl or Br, L = L3; n= 0, X = Cl, L = L4; n= 2, X = Br, L = L4) and a binuclear complex [Pd(cotl)Br]2L2. The complexes were characterised by physical properties, i.r., 1H- and 13C-n.m.r. spectral techniques and by mass spectra. Probable structures have been proposed.  相似文献   

2.
By reacting [Pd( )(μ-Cl)]2 with AgClO4 in NCMe, the corresponding cationic complexes [Pd( )(NCMe)2]ClO4 ( = phenylazophenyl-C2,N1; dimethylbenzylamine-C2,N; 8-methylquinoline-C8,N) can be obtained. Solutions containing the cations [Pd( )(S)2]+ are obtained when the reaction is carried out in tetrahydrofuran or acetone (S). The treatment of these solutions with bidentate ligands (L—L) (Ph2PCH2PPh2,Ph2PNHPPh2 or Ph2PCH2PPh2CHC(O)Ph) gives the mononuclear [Pd( )(L3l)]ClO4 complexes, with L3l acting as a chelate ligand. On the other hand [Pd( (μ-Cl)]2 reacts with L3l (Ph2PCH2PPh2, Ph2PNHPPh2) yielding [Pd( )Cl(L3l)] with L3l acting as monodentate. The reactions between [Pd( )(NCMe)2]ClO4 and 2,2′-bipyrimidyl give rise to the formation of the mononuclear [Pd( ) (bipym)]ClO4 or binuclear [Pd2( )2(μ-bipym)](ClO4)2, [( )Pd(μ-bipym)Pd( )](ClO4)2 derivatives. Finally [Pd( )Cldppm] (dppm = Ph2PCH2PPh2) react with NaH producing the neutral complexes [Pd( )(ddppm)] (ddppm = Ph2PCHPPh2) which by reaction with HCl lead again to the starting materials [Pd( )Cl(dppm)].  相似文献   

3.
Cationic pentafluorophenyl palladium(II) complexes of the type [Pd(C6F5)L2(APPY)]ClO4 (L = PPh3, PBu3n; L2 = bipy and A acetylmethylenetriphenylphosphorane) have been prepared by addition of APPY to the perchlorato complexes [Pd(OClO3)(C6F5)L2]; the APPY ligand is O-coordinated, which is unprecedented in keto-stabilized ylide complexes of palladium.The neutral complex Pd(C6F5)(Cl)(tht)(APPY) has been made by addition of APPY to the binuclear complex Pd2(μ-Cl)2(C6F5)2(tht)2 (tht = tetrahydrothiophene); in which the APPY ligand shows the normal C-coordination.  相似文献   

4.
Ni(II) mononuclear dithiocarbamate complexes with bidentate P,P ligands of composition [Ni(R2dtc)(P,P)]X {R?=?pentyl (pe), benzyl (bz); dtc?=?S2CN?; P,P?=?1,2-bis(diphenylphosphino)ethane (dppe), 1,4-bis(diphenylphosphino)butane (dppb), 1,1′-bis(diphenylphosphino) ferrocene (dppf); X?=?ClO4, Cl, Br, NCS} and binuclear complexes of composition [Ni2(μ-dpph)(R2dtc)2]X2 with a P,P-bridging ligand {P,P?=?1,6-bis(diphenylphosphino)hexane (dpph); X?=?Cl, Br, NCS} have been synthesized. The complexes have been characterized by elemental and thermal analysis, IR, electronic and 31P{1H}-NMR spectroscopy, magnetochemical and conductivity measurements. Single crystal X-ray analysis of [Ni(pe2dtc)(dppf)]ClO4 confirmed a distorted square planar coordination in the NiS2P2 chromophore. For selected samples, the catalysis of graphite oxidation was studied.  相似文献   

5.
《Polyhedron》1987,6(6):1427-1431
Mono- and dinuclear rhodium(I) complexes of formulae [Rh(L2)(bipym)]+ and [{Rh(L2)}2(μ-bipym)]2+ [L2 = diolefin or (CO)2] have been prepared and their catalytic activity in hydrogen-transfer reactions explored. The heterodinuclear [Cl2Pd(μ-bipym)Rh(tfb)]ClO4 complex was obtained by reacting [Rh(tfb)(bipym)]+ with [PdCl2(cod)] or alternatively from [Rh(tfb)(acetone)x]+ with [PdCl2(bipym)]. Ion-pair complexes of formulae [Rh(diolefin)(bipym)]+ [RhCl2(diolefin)] (diolefin = cod, nbd or tfb) were prepared by adding bipym to acetone suspensions of [RhCl(diolefin)]2.  相似文献   

6.
Four new ternary complexes: [Cu(IP)(L-Val)(H2O)]ClO4·1.5H2O(1), [Cu(IP)(L-Leu)(H2O)]ClO4(2), [Cu(IP)(L-Tyr)(H2O)]ClO4·H2O(3) and [Cu(IP)(L-Trp)(H2O)]ClO4·1.5H2O(4) have been synthesized and character/zed by elementa/analysis, molar conductivity, infrared absorption spectroscopy, electronic absorption spectroscopy and cyclic voltammetry, where IP=imidazo[4,5-f][1,10] phenanthroline, L-Val=L-valinate, L-Leu=L-leucinate, L-Tyr=L-tyrosinate and L-Trp=L-tryptophanate. Complex 3 was structurally characterized by X-ray diffraction method, which crystallizes in orthorhornbic space group P21212 in a unit cell of dimensions a=3.0567(4) nm, b=0.74079(9) nm, c= 1.06198(13) nm, V=2.4047(5) nm^3, Z=4,μ=0.1084 cm^-1. The SOD-like activities of catalytic disrnutation of superoxide anions (O2^-· ) by the complexes were determined by means of modified nitroblue tetrazolium (NBT) photoreduction. The IC50 values of complexes 1, 2, 3 and 4 are 0.072, 0.147, 0.429 and 0.264 μmol·L^-1, respectively  相似文献   

7.
Two macrocyclic Schiff base ligands, L1 [1+1] and L2 [2+2], have been obtained in a one-pot cyclocondensation of 1,4-bis(2-formylphenyl)piperazine and 1,3-diaminopropane. Unfortunately, because of the low solubility of both ligands, their separation was unsuccessful. In the direct reaction of these mixed ligands (L1 and L2) and the appropriate metal ions only [CoL1(NO3)]ClO4, [NiL1](ClO4)2, [CuL1](ClO4)2 and [ZnL1(NO3)]ClO4 complexes have been isolated. All the complexes were characterized by elemental analyses, IR, FAB-MS, conductivity measurements and in the case of the [ZnL1(NO3)]ClO4 complex with NMR spectroscopy.  相似文献   

8.
The reaction of [OsX2(HL)(L)] (1) {X = Cl or Br; HL = PhC(O)C(=NOH)Ph (HL1) or PhC(O)C(=NOH)Me (HL2)] with n-BuONO yields mononuclear [OsX(NO)(L1)2] (2) or binuclear [OsX2(NO)(L2)]22 (3) nitrosyls depending on L. The complexes are also obtained by reacting (1) with NaNO2 plus HCl. Molecular weight determinations are in agreement with mono- and binuclear formulations. The diamagnetic orange-red nitrosyls exhibit (NO) at ca. 1890 cm–1 indicating NO+ character of the bound nitrogen monoxide. In 1H-n.m.r. a single sharp L2 methyl signal is in line with the centrosymmetric geometry (4) of the binuclear nitrosyls. The complexes display both spin-allowed and -forbidden charge transfer transitions in the 1000–200 nm range. Both (2) and (3) are electroactive and reductions characteristic of mono- and binuclear compositions are observable on the negative side of s.c.e. They react smoothly with acetylacetone (acacH) in the presence of K2CO3 yielding K[Os(acamo)(L1)2] (5) and K[Os(acac)(acamo)(L2)] (6) [acamo = deprotonated MeC(O)C(=NOH)C(O)Me] respectively.  相似文献   

9.
Novel dihydroiridium(III) complexes containing mono- and bi-dentate sulfur ligands have been isolated. The cationic complexes [Ir(COD)L2]ClO4 (COD = 1,5-cyclooctadiene, L = tetrahydrothiophene (tht) or trimethylene sulfide (tms); L2 = (CH3S)2(CH2)3 (dth)), [Ir(COD)(L-L)]2(ClO4)2 (L-L = 1,4-dithiacyclohexane (dt) or (t-BuS)2(CH2)2 (tmdto)) and [Ir(CO)2(tmdto)]2-(ClO4)2 react with H2 to give the corresponding iridium(III) dihydrides: [IrH2COD)L2]ClO4 (Ia: L = tht, Ib: L = tms, Ic: L2 = dth), [IrH2(COD)-(L-L)]2(ClO4)2 (IIa: L-L = tmdto, IIb: L-L = dt) and [IrH2(CO)2(tmdto)]2-(ClO4)2 (III). The 1H NMR chemical shifts and ν(IrH) data are discussed.  相似文献   

10.
Jin Yang 《Tetrahedron》2019,75(14):2182-2187
A series of mixed N-heterocycles/N-heterocyclic carbene palladium(II) allyl complexes with general formula [(NHC)Pd(η3-allyl)]2(μ2-N-heterocycles)(BF4)2 were prepared in one pot based on anion metathesis of (NHC)Pd(η3-allyl)Cl complexes and then ligand replacement with N-heterocycles [N-heterocycles?=?pyrazine (pyz), 4,4′-bipyridine (bpy) and trans-4,4′-bipyridylethylene (bpe)]. The solid-state structures shown dinuclear structures with two palladium(II) centers holding together by bridged N-heterocycles. Initially investigation of the obtained complexes as precatalysts for direct CH bond arylation of azoles with aryl bromides was carried out.  相似文献   

11.
Complexes with Macrocyclic Ligands. IV. Heterodinuclear Cobalt(II), Nickel(II), Copper(II), Zinc(II) and Palladium(II) Complexes with a Macrocyclic Ligand of Schiff‐Base Type: Syntheses and Structures The synthesis and properties of nickel(II), copper(II), and palladium(II) complexes, [MLPh] ( 3 ; LPh = N,N′‐phenylene‐bis(3‐formyl‐5‐tert.‐butyl‐salicylaldimine)), are described. These neutral mononuclear complexes react with metal(II) perchlorate and 1,3‐propylenediamine to form heterodinuclear, macrocyclic, cationic complexes of the type [MM′(LPh,3)]2+ ( 4 ; M = Ni, Cu, Pd; M′ = Co, Cu, Zn). The structures of the five new compounds [NiCo(LPh,3)](ClO4)2, [NiCu(LPh,3)](ClO4)2, [CuCu(LPh,3)](ClO4)2, [CuZn(LPh,3)](ClO4)2, and [PdCu(LPh,3)](ClO4)2 were determined by X‐ray diffraction.  相似文献   

12.
This paper discusses coordination-position isomeric MIICuII and CuIIMII complexes, using unsymmetric dinucleating macrocycles (Lm;n)2− ((L2;2)2−, (L2;3)2− and (L2;4)2−) that comprise two 2-(N-methyl)-aminomethyl-6-iminomethyl-4-bromo-phenonate entities, combined through the ethylene chain (m = 2) between the two amine nitrogens and through the ethylene, trimethylene or tetramethylene chain(n = 2, 3 or 4) between the two imine nitrogens. The macrocycles have dissimilar N(amine)2O2 and N(imine)2O2 metal-binding sites sharing the phenolic oxygens. The reaction of the mononuclear CuII precursors, [Cu(L2;2)], [Cu(L2;2)] and [Cu(L2;2)], with a MII perchlorate and a MII acetate salt formed (acetato)MIICuII complexes: [CoCu(L2;2)(AcO)]ClO4·0.5H2O] (1), [NiCu(L2;2) (AcO)]ClO4 (2), [ZnCu(L2;2) (AcO)]ClO4 (3), [CoCu(L2;3)(AcO)]ClO4·0.5H2O (4), [NiCu(L2;3)(AcO)]ClO4 (5), [ZnCu(L2;3)(AcO)]ClO4·0.5H2O (6), [CoCu(L2;4)(AcO)(DMF)]ClO4 (7), [NiCu(L2;4) (AcO)]ClO4·2DMF (8) and [ZnCu(L2;4)(AcO)]ClO4 (9) (the formulation [MaMb (Lm;n)]2+ means that Ma resides in the aminic site and Mb in the iminic site). The site selectivity of the metal ions is demonstrated by X-ray crystallographic studies for 2·MeOH,3,5,7, and9. An (acetato)CuIIZnII complex, [CuZn(L2;3)(AcO)]ClO4 (10), was obtained by the reaction of [PbCu(L2;3)]-(ClO4)2 with ZnSO4·4H2O, in the presence of sodium acetate. Other complexes of the CuIIMII type were thermodynamically unstable to cause a scrambling of metal ions. The Cu migration from the iminic site to the aminic site in the synthesis of10 is explained by the ‘kinetic macrocyclic effect’. The coordination-position isomers,6 and10, are differentiated by physicochemical properties.  相似文献   

13.
The reactions of dl‐proline with chiral macrocyclic NiII complex [Ni(SSL)](ClO4)2 in acetonitrile/water gave a six‐coordinate enantiomer formulated as [Ni(SSL)(l‐Pro)](ClO4)2 · H2O ( 1 ). Another enantiomer of [Ni(RR‐L)(d‐Pro)](ClO4)2 · H2O ( 2 ) was obtained when [Ni(RR‐L)](ClO4)2 was used (L = 5,5,7,12,12,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane, Pro = proline). Single‐crystal X‐ray diffraction analyses of complexes 1 and 2 revealed that the NiII atom has a distorted octahedral coordination arrangement, being coordinated by four nitrogen atoms of L in a folded configuration, plus two carboxylate oxygen atoms of proline in mutually cis positions. Complexes 1 and 2 are supramolecular stereoisomers, which are constructed with hydrogen bonding linking of [Ni(SS‐L)(l‐Pro)]2+ and [Ni(RR‐L)(d‐Pro)]2+ monomers to form one‐dimensional zigzag chains. The homochiral natures of complexes 1 and 2 were confirmed by solid CD spectroscopy.  相似文献   

14.
The 2-picolylpalladium(II) complex [{Pd(CH2Py)Cl(PPh3)}2] (CH2Py=2-picolyl) (I), prepared from 2-picolyl chloride and [Pd(PPh3)4], was treated with lithium bromide, silver acetate, 4-picoline (pic) and silver perchlorate, thallium acetylacetonate{Tl(acac)}, sodium dimenthyldithiocarbamate-water-(1/2) {Na(dmdc). 2 H2O}, and 1,2-bis(diphenylphospino)ethane (dppe) to yield [{PdBr(CH2Py)(PPh3)}2] (II), [{Pd(CH2Py)OAc(PPh3)}2] (III), [{Pd(Ch2Py)(pic)(PPh3)}2](ClO4)2 (IV), [Pd(CH2Py)(acac)(PPh3)] (V), [Pd(CH2Py)(dmdc)(PPh3)] (VI), and [Pd(Ch2Py)Cl(dppe)] (VII), respectively. Halogen abstraction from VII using silver perchlorate afforded an ionic complex [{Pd(CH2Py)(dppe)}2](ClO4)2 (VIII). It was concluded that the 2-picolyl groups in these eight complexes are σ-bonded to palladium, and that in the dinuclear complexes I, II, III, IV, and VIII, they serve as bridging ligands.  相似文献   

15.
Mono-and binuclear cyclopalladated complexes [Pd(ppm)En]ClO4, [Pd(Hdphpm)En]ClO4, and [(PdEn)2(μ-dphpm)]ClO4 (ppm? is the deprotonated form of 4-phenylpyridine, Hdphpm? and dphpm2? are the mono-and bisdeprotonated forms of 4,6-diphenylpyrimidine, En is 1,2-diaminoethane) were prepared and characterized by means of 1H NMR and electronic absorption and emission spectroscopy, and cyclic voltammetry. It was shown that cyclopalladation leads to a bathochromic shift of intraligand absorption and phosphorescence bands, appearance of new absorption band associated with metal-to-ligand charge transfer, and an anodic potential shift of the ligand-centered electroreduction Hppm ≈ H2dphpm < [Pd(ppm)En]+ ≈ [Pd(Hdphpm)En]+ < [(PdEn)2(μ-dphpm)]2+.  相似文献   

16.
A new benzimidazoyl ligand bis[(N-ethylbenzimidazol-2-yl)methyl]ether (EDGB) and CuII complexes [Cu(L1) (L2)](ClO4)·mEt2O·nH2O [L1 = bis[(benzimidazol-2-yl)methyl]ether (DGB) or EDGB, L2 = 2,2-bipyridine (bipy) or 1,10-phenanthroline (phen)] have been synthesized and characterized by elemental analyses and i.r. spectra. The single-crystal structure of the [Cu(phen)(DGB)(OClO3)]ClO4·Et2O·0.5H2O complex was determined by X-ray diffraction. The geometry around Cu is best described as a distorted octahedron with four nitrogen atoms from phen and DGB ligands forming the equatorial plane. The oxygen atoms of DGB and one perchlorate group are in the axial positions with semi-coordinated bonding modes. The electrochemical behavior of the complexes is described.  相似文献   

17.
Cationic rhodium(I) complexes of the general formula [Rh(COD)L2]ClO4 (L2 = bipyO2, phenO, dpeO2 and dpmO2) are prepared from the solvated species [Rh(COD)(Me2CO)x]+ and the appropriate ligand. Complexes of the type [Rhn(COD)n](ClO4)n (CNPyO = 4-cyano and 2-cyanopyridine N-oxide) are obtained similarly. Reaction of [RhCl(COD)]2 with the potassium salt of 2-picolinic acid N-oxide leads to the neutral complex Rh(COOPyO)(COD). The mononuclear rhodium diolefinic compounds react with carbon monoxide to give complexes of the type [Rh(CO)2L2]ClO4 and Rh(COOPyO)(CO)2, which on treatment with triphenylphosphine yield monocarbonyl derivatives.The catalytic activities of the diolefin complexes and related derivatives in hydrogen-transfer catalytic reactions have been studied.  相似文献   

18.
Pd(MME)Cl2 complex, where MME = methionine methyl ester, was synthesized and characterized by elemental analysis and spectroscopic techniques. [Pd(MME)(H2O)2]2+ interacts with some DNA constituents giving 1 : 1 and 1 : 2 complexes. The binuclear complexes having 4,4′-bipiperidine as a linker and involving [Pd(MME)(H2O)2]2+ and DNA constituents were investigated. The results show formation of [(H2O)(MME)Pd(Bip)Pd(MME)(H2O)]4+. Inosine, uracil, and thymine interact with the previously mentioned complex by substitution of the two coordinated water molecules. Formation constants of all possible mono- and binuclear complexes were determined and their speciation diagrams were evaluated.  相似文献   

19.
The [M(dithiocarbamato)(Mol)]Cl complexes [M = Pd or Pt; dithiocarbamato = DMDT (Me2NCS 2) or ESDT (EtO2CCH2MeNCS 2); Mol = L-methioninol (L-2-amino-4-methylthio-1-butanol)] have been prepared by reacting methioninol with the appropriate [M(dithiocarbamato)Cl] n complex in a 1:1 molar ratio in chlorinated hydrocarbons. By operating at a 1:2 molar ratio, the binuclear species [M2(dithiocarbamato)2(Mol)Cl2] were obtained. The complexes were characterized by i.r., n.m.r. and electrospray ionisation (ESI) mass spectra and by t.g.a. The [M(dithiocarbamato)(Mol)]Cl species are ionic and contain S,N-chelated methioninol. The ligand forms an S,N bridge between two metal atoms in the binuclear species, whose formation is confirmed by the presence of the deprotonated molecular ion in the ESI negative ion mode.  相似文献   

20.
In search of new DNA probes a series of new mono and binuclear cationic complexes [RuH(CO)(PPh3)2(L)]+ and [RuH(CO)(PPh3)2(-μ-L)RuH(CO)(PPh3)2]2+ [L=pyridine-2-carbaldehyde azine (paa), p-phenylene-bis(picoline)aldimine (pbp) and p-biphenylene-bis(picoline)aldimine (bbp)] have been synthesized. The reaction products were characterized by microanalyses, spectral (IR, UV-Vis, NMR and ESMS and FAB-MS) and electrochemical studies. Structure of the representative mononuclear complex [RuH(CO)(PPh3)2(paa)]BF4 was crystallographically determined. The crystal packing in the complex [RuH(CO)(PPh3)2(paa)]BF4 is stabilized by intermolecular π-π stacking resulting into a spiral network. Topoisomerase II inhibitory activity of the complexes and a few other related complexes [RuH(CO)(PPh3)2(L)]+ {L=2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) and 2,3-bis(2-pyridyl)-pyrazine (bppz)} have been examined against filarial parasite Setaria cervi. Absorption titration experiments provided good support for DNA interaction and binding constants have also been calculated which were found in the range 1.2 × 103-4.01 × 104 M−1.  相似文献   

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