共查询到20条相似文献,搜索用时 46 毫秒
1.
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
2.
T. A. Tkacheva O. A. Farus M. P. Puzyk K. P. Balashev 《Russian Journal of General Chemistry》2008,78(4):668-672
Comparative study of cyclopalladated ethylenediamine complexes of 2,3-diphenylquinoxaline (Hdphqx) [Pd(dphqx)En]ClO4 and 2,2′,3,3′-tetraphenylbiquinoline (H2tphbq) [(PdEn)2(μ-tphbq)](ClO4)2, and the free heterocyclic ligands was performed by means of 1H NMR spectroscopy, electronic absorption and emission spectroscopy, and cyclic voltammetry. It was shown that cyclopalladation gives rise to a long-wave absorption band in the visible spectrum, a batochromic shift of the vibrationally structured phosphorescence band, and an anodic shift of the ligand-centered reduction potential of the complexes com-pared to free ligands. 相似文献
3.
Katlenok E. A. Puzyk M. V. Balashev K. P. 《Russian Journal of General Chemistry》2011,81(8):1711-1715
The 1H NMR, electronic absorption, and luminescence spectra, as well as voltammograms of the reduction and oxidation of the complexes
[Pd(C∧N)(N∧N)]ClO4 and [Pd(C∧N)(μ-OOCCH3)]2 [where (C∧N)− is deprotonated 2-phenyl-4,5-dihydro-1,3-oxazole, and N∧N is ethylenediamine or 2,2′-bipyridine (bpy)] were compared. Magnetic
nonequivalence of protons in the dihydrooxazole ring and upfield shift of the corresponding signals were observed as a result
of anisotropic effect of the ring current in palladated phenyl substituents in the [Pd(C∧N)(μ-OOCCH3)]2 complex having a C
2 symmetry. One-electron reduction wave of [Pd(C∧N)bpy]+ was assigned to ligand-centered electron transfer to the π* orbital of 2,2′-bipyridine, and two oxidation waves of [Pd(C∧N)(μ-OOCCH3)]2 were attributed to successive one-electron oxidations of the palladium centers. Low-temperature (77 K) phosphorescence of
[Pd(C∧N)En]+ and [Pd(C∧N)bpy]+ was ascribed to optical transition localized on the metal-complex fragment {Pd(C∧N)} and to interligand charge transfer between
the chelating and cyclopalladated ligands. The formation of metal-metal bond in the complex [Pd(C∧N)(μ-OOCCH3)]2 gives rise to radiative decay of photoexcitation energy from two electronically excited states, one of which is localized
on the {Pd(C∧N)} fragment, and the second corresponds to the charge transfer metal-metal-cyclopalladated ligand. 相似文献
4.
E. V. Ivanova M. V. Puzyk K. P. Balashev 《Russian Journal of General Chemistry》2009,79(10):2096-2101
Biscyclometallated [(M(N∧N))2(μ-dphpm)](ClO4)2 and [(N∧N)Pd(μ-dphpm)Pt(N∧N)]Cl2 complexes [M = Pd(II), Pt(II); (N∧N) ethylenediamine (En), 1,10-phenanthroline (phen); dphpm2 — bisdeprotonated form of 4,6-diphenylpyrimidine)] have been characterized by the 1H NMR, electronic absorption and emission spectroscopy, and also cyclic voltammetry methods. The lowest unoccupied molecular
orbital (LUMO) of biscyclometallated complexes with ethylenediamine, responsible for low-energy photo- and electro-stimulated
processes irrespective of the metal nature, is assigned to the π* orbital mainly localized on the pyrimidine part of the bridging
ligand. In the case of complexes with phenanthroline chelating ligands, the replacement of one or two palladium metal centers
[{Pd(phen)}2(μ-dphpm)]2+ by platinum centers changes the LUMO nature of the complexes for the π* orbital mainly localized on the peripheral metal-complex
fragment {Pt(phen)}. 相似文献
5.
Zou Jianzhong Wu Yong Duan Chunyin Liu Yongjiang Xu Zheng 《Transition Metal Chemistry》1998,23(3):305-308
Three binuclear copper(II) complexes bridged by three different bridging ligands: μ-TPHA (terephthalato), μ-PHTA (phthalato)
and μ-TCB (tetracarboxylatobenzene) have been synthesized. The crystal structure of [{Cu(dipn)}2(μ-TPHA)](ClO4)2 where dipn = N-(3-aminopropyl)-1,3-propanediamine was solved at room temperature. The [{Cudipn}2(μ-TPHA)](ClO4)2 complex consists of a μ-terephthalato bridging binuclear copper(II) cationic unit and two non-coordinated perchlorate anions.
The TPHA ligand bridges in a bismonodentate fashion. The environment of the copper(II) ion is a distorted plane-square-planar coordination sphere. The magnetic
properties of the three complexes have been investigated in the 75–300 K range, and show that the geometry of the CuII atom is the important factor for magnetic interactions in the terephthalato bridging binuclear copper(II) complexes.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
6.
Santana A. M. Mauro A. E. Zorel H. E. Mattioli M. P. D. de Lucca Neto V. A. 《Journal of Thermal Analysis and Calorimetry》2002,67(2):425-431
The dimeric compound [Pd(bzan)(μ-OOCCH3)]2 (1) (bzan=N-benzylideneaniline) reacts with KX, in methanol/acetone (2:1), affording the analogous dimeric pseudohalogen-bridged species
[Pd(bzan)(μ-X)]2 [X=NCO(2),SCN(3), CN(4)]. The compounds were characterized by elemental analysis, infrared spectroscopy, NMR and thermogravimetric
analysis. IR data for 2–4 showed bands typical of coordinated pseudohalogen ligands clearly indicating the occurrence of the
exchange reaction. Their thermal behaviour was investigated and suggested that their stability is influenced by the bridging
ligand. The thermal stability decreased in the order[Pd(bzan)(μ-CN)]2>[Pd(bzan)(μ-SCN)]2>[Pd(bzan)(μ-OOCCH3)]2>[Pd(bzan)(μ-NCO)]2. X-ray results showed the formation of Pd° as final decomposition product.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
7.
Two similar tetranuclear copper(II) complexes with the formulae [Cu4(L1)2(μ1,1-N3)4(μ2-CH3COO)2] and [Cu4(L2)2(μ1,1-N3)2(μ-Br)2Br2(CH3OH)2], where L1 and L2 are the deprotonated forms of 2-[(2-ethylaminoethylimino)methyl]-5-methoxyphenol and 5-methoxy-2-[(2-piperidin-1-ylethylimino)methyl]phenol,
respectively, have been synthesized and characterized by spectroscopic methods and single-crystal X-ray diffraction. Both
complexes are centrosymmetric tetranuclear copper(II) compounds. The bridging groups in [Cu4(L1)2(μ1,1-N3)4(μ2-CH3COO)2] are μ1,1-azide ligands and μ2-acetate ligands, and those in [Cu4(L2)2(μ1,1-N3)2(μ-Br)2Br2(CH3OH)2] are μ1,1-azide ligands and μ-bromide ligands. Each Cu atom in the complexes is in a square pyramidal geometry. 相似文献
8.
Complexes [Pd(bt)(4,4′-bpy)OOCCH3], [Pd(bt)NO3]2(m-4,4′-bpy), [Pd(bt)(m-4,4′-bpy)]4(NO3)4 (bt− is deprotonated form of 2-phenylbenzothiazole, bpy is 4,4′-bipyridyl) are prepared and characterized by 1H NMR, electron absorption and emission spectroscopy, as well as by voltammetry. The upfield shift of the signal of proton
in the ortho-position to the donor carbon atom of the cyclopalladated ligand in the complexes [(Δδ = −(1.1–1.5) ppm] is assigned to the
anisotropic effect of the ring current of the pyridine rings of the 4,4′-bipyridyl moiety, which are orthogonal to the coordination
plane. Characteristic longwave absorption bands λ = (387±4) nm and the low-temperature phosphorescence bands λ = (512±3) nm
in the complexes are assigned to the chromophore {Pd(bt)} metal complex fragment. The reduction waves in the complexes [E
1/2 = −(1.54±0.04) and E
p = −(1.83±0.03) V] are assigned to the ligand-centered processes of the successive electron transfer to the π* orbitals localized
predominantly on the coordinated pyridine components of the 4,4′-bipyridyl moiety. 相似文献
9.
《Polyhedron》1999,18(20):2597-2603
Macrotetracyclic complexes of nickel(II) containing crown ethers as pendant arms, [Ni(B)](ClO4)2 and [Ni(C)](ClO4)2, were prepared and characterized. The binding constants of the complexes toward alkali metal ions are relatively small compared with those of free 15-crown-5 or 18-crown-6 and the reduction potentials of the [Ni(B)](ClO4)2 and [Ni(C)](ClO4)2 in the presence of alkali metal ions shift to the positive direction in the order Li+>Na+>K+ and K+>Na+>Li+, respectively. 相似文献
10.
Three novel unsymmetric tridentate ligands, namely, ptmi (ptmi = 3-(1,10-phenanthroline-2-yl)-as-triazino[5,6-f]-5-methoxyisatin), pti (pti = 3-(1,10-phenanthroline-2-yl)-as-triazino-[5,6-f]isatin), ptni (ptni = 3-(1,10-phenanthroline-2-yl)-as-triazino[5,6-f]-5-nitroisatin), and their complexes [Ru(tpy)(ptmi)](ClO4)2 (tpy = 2,2′:6′,2″-terpyridine) (1), [Ru(tpy)(pti)](ClO4)2 (2), and [Ru(tpy)(ptni)](ClO4)2 (3) were prepared and characterized by elemental analysis, 1H NMR, ES–MS. The electrochemical behaviors were studied by cyclic voltammetry. The DNA-binding properties of these complexes
were investigated by the spectroscopic method, viscosity measurements, and thermal denaturation. Theoretical studies on these
complexes were also performed with the density functional theory (DFT) method. The experimental results showed that these
complexes bind to calf thymus (CT-DNA) in an intercalative mode. The order of DNA-binding affinities (A) of these complexes is A(1) < A(2) < A(3). The trend in the DNA-binding affinities of this series of complexes can be reasonably explained by the DFT calculations. 相似文献
11.
Subhi A. Al-Jibori Ali I. Abdullah Talal A. K. Al-Allaf 《Transition Metal Chemistry》2007,32(3):398-406
Palladium(II) and platinum(II) complexes containing mixed ligands N-(2-pyridyl)acetamide (AH) or N-(2-pyrimidyl)acetamide (BH) and the diphosphines Ph2P(CH2)
n
PPh2, (n = 1, 2 or 3) have been prepared. The prepared complexes [Pd(A)2(diphos)] or [Pd(B)2(diphos)] have been used effectively to prepare bimetallic complexes of the type [(diphos)Pd(μ-L)2M′Cl2] where M′ = Co, Cu, Mn, Ni, Pd, Pt or SnCl2; L = A or B. The prepared complexes were characterized by elemental analysis magnetic susceptibility, i.r. and UV–Vis spectral
data. 31P–{1H}-n.m.r. data have been applied to characterize the produced linkage isomers. 相似文献
12.
S. E. Nefedov N. Yu. Kozitsyna N. S. Akhmadullina N. V. Cherkashina M. N. Vargaftik I. I. Moiseev 《Russian Journal of Inorganic Chemistry》2011,56(3):357-374
The reactions of palladium(II) acetate with neodymium(III) and cerium(III) acetates in acetic acid containing a specified
amount of water have been studied. The following homo- and heterometallic complexes have been synthesized and characterized
by X-ray diffraction: Nd2(μ-OOCMe)2(μ,η2-OOCMe)2(η2-OOCMe)2(HOOCMe)2(OH2)2 · 4HOOCMe, [Pd(μ-OOCMe)4Ce(OH2)2(μ,η2-OOCMe)]2 · 2HOOCMe · 6H2O, [Pd(μ-OOCMe)4Ce(OH2)2(μ,η2-OOCMe)]2 · 14H2O, [Pd(μ-OOCMe)4M(HOOCMe)2(OH2)2]+ [Pd(μ-OOCMe)4M(μ-OOCMe)4Pd]− · 2MeCOOH · 1.5H2O (M = Nd, Ce), and {[Pd(μ-OOCMe)4Ce(OOCMe)4]2 [Pd4(μ-OOCMe)4]2(μ4-O)8CePd4}(OH)3 · 27H2O. From kinetic and structural data and optical spectra of reaction solutions, the conclusion was drawn that hydrolytic processes
play a decisive role in complexation reactions. 相似文献
13.
Y. M. Dan Y. R. Zhao Y. Liu S. S. Qu 《Journal of Thermal Analysis and Calorimetry》2006,84(3):531-534
The two complexes, [Ln(Ala)2(Im)(H2O)](ClO4)3 (Ln=Pr,
Gd), were synthesized and characterized. Using a solution-reaction isoperibol
calorimeter, standard enthalpies of reaction of two reactions: LnCl3⋅6H2O(s)+2Ala(s)+Im(s)+3NaClO4(s)=[Ln(Ala)2(Im)(H2O)](ClO4)3(s)+3NaCl(s)+5H2O(l) (Ln=Pr, Gd),
at T=298.15 K, were determined to be (39.26±0.10)
and (5.33±0.12) kJ mol–1 , respectively.
Standard enthalpies of formation of the two complexes at T=298.15
K, ΔfHΘm
{[Ln(Ala)2(Im)(H2O)](ClO4)3(s)} (Ln=Pr, Gd),
were calculated as –(2424.2±3.3) and –(2443.4±3.3)
kJ mol–1 , respectively. 相似文献
14.
V. A. Lucca Neto A. E. Mauro A. V. G. Netto A. C. Moro V. M. Nogueira 《Journal of Thermal Analysis and Calorimetry》2009,97(1):57-60
The cyanate-bridged cyclopalladated compound [Pd(C2,N-dmba)(μ-NCO)]2 (dmba=N,N-dimethylbenzylamine) reacts in acetone with pyrazole (pz), 3,5-dimethylpyrazole (dmpz), imidazole (imz) and 2-methylimidazole
(mimz) to give [Pd2(C2,N-dmba)2(μ-NCO)(μ-pz)] (1), [Pd2(C2,N-dmba)2(μ-NCO)(μ-dmpz)] (2), [Pd(C2,N-dmba)(NCO)(imz)] (3) and [Pd(C2,N-dmba)(NCO)(mimz)] (4), respectively. The compounds were characterized by elemental analysis, IR spectroscopy and TG. The thermal decomposition
of the compounds occurs in three consecutive steps and the final decomposition products were identified as Pd(0) by X-ray
powder diffraction. The thermal stability order of the complexes is 2>3>1>4. 相似文献
15.
Two copper(I) complexes [Cu(Cin2bda)2]ClO4 (I) and [Cu(Ncin2bda)2]ClO4 (II) have been prepared by the reaction of the ligands N2,N2′-bis(3-phenylallylidene)biphenyl-2,2′-diamine (L1) and N2,N2′-bis[3-(2-nitrophenyl)allylidene]biphenyl-2,2′-diamine (L2) and copper(I) salt. These compounds were characterized by CHN analyses, 1H NMR, IR, and UV-Vis spectroscopy. The C=N stretching frequency in the copper(I) complexes shows a shift to a lower frequency
relative to the free ligand due to the coordination of the nitrogen atoms. The crystal and molecular structure of II was determined
by X-ray single-crystal crystallography. The coordination polyhedron about the copper(I) center in the complex is best described
as a distorted tetrahedron. A quasireversible redox behavior was observed for complexes I and II.
The article is published in the original. 相似文献
16.
《Polyhedron》1986,5(6):1213-1216
The square planar complexes cis-[MCl2(hypy)], cis-[MCl2(hyqu)], [Pt(hypy)2] [PtCl4], [Pd(hypy)2][ClO4]2 and [Pd(hyqu)2][ClO4]2 (M = Pd or Pt, hypy = 2-hydrazinopyridine, hyqu = 8-hydrazinoquinoline), in which hypy and hyqu act as bidentate chelating ligands, have been prepared and characterized. Complexes containing hyqu do not appear to have been isolated previously. 相似文献
17.
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
18.
Abstract
Three copper(II), one zinc(II), and one ferrous(II) complexes having 3-bromo or 3,8-dibromo-1,10-phenanthroline ligand with different metal/ligand molar ratios, formulated as [Cu(3-bromo-phen)(ClO4)(C3H7NO)2(H2O)](ClO4) (1), [Cu(3,8-dibromo-phen)(ClO4)(C3H7NO)2(H2O)](ClO4) (2), [Cu(3,8-dibromo-phen)(ClO4)(H2O)3](ClO4)(H2O)3 (3), [Zn(3,8-dibromo-phen)2(H2O)2](ClO4)2(H2O)2 (4), and [Fe(3,8-dibromo-phen)3](ClO4)2(H2O)(CH4O)(C3H6O)2 (5) (phen = 1,10-phenanthroline), have been synthesized and characterized in this paper. X-ray single-crystal diffraction studies reveal the different crystallographic symmetry and packing fashions between neighboring phen rings in 1:1 Cu(II) complexes 1–3 due to the alteration of bromo substituent 1,10-phenanthroline ligands and coordinated or free solvent molecules. Additionally, in 1:2 Zn(II) and 1:3 Fe(II) complexes 4 and 5, continuous π–π stacking and alternating π–π and dimeric p–π stacking are found. 相似文献19.
A. V. G. Netto Regina C. G. Frem A. E. Mauro Marisa S. Crespi H. E. Zorel Jr 《Journal of Thermal Analysis and Calorimetry》2007,87(3):789-792
Synthesis, spectroscopic characterization
and thermal behavior of pyrazolate-bridged palladium complexes [Pd(μ-Pz)2]n
(1), [Pd(μ-mPz)2]n
(2), [Pd(μ-dmPz)2]n
(3), [Pd(μ-IPz)2]n
(4) {pyrazolate (Pz–),
4-methylpyrazolate (mPz–), 3,5-dimethylpyrazolate
(dmPz–), 4-iodopyrazolate (IPz–)}
have been described in this work. The exobidentate coordination mode of pyrazolato
ligands in 1–4
was inferred on basis of IR spectroscopic evidences. TG investigations indicated
that the introduction of substituents at the 4 position in the pyrazolyl moiety
into coordination polymers do not affect significantly their thermal stability,
whereas at the 3 and 5 position reduced the stability of the main chain. Metal
palladium was the final product of the thermal decompositions, which was identified
by X-ray powder diffraction. 相似文献
20.
Platinum group metal chalcogenides find extensive applications in catalysis and in the electronic industry. To develop an
efficient low temperature clean preparation of these materials, molecular routes have been explored. Thus the chemistry of
mononuclear organochalcogenolates of the type [M(ER’)2(PR3)2], binuclear benzylselenolates, [M2Cl2(μ-SeBz)2(PR3)2], allylpalladium complexes [Pd2(μ-ER)2(η3-C4H7)2] and palladium/platinum sulphido/selenido-bridged complexes, [M2(μ-E)2L4] (M = Pd or Pt; E = S, Se or Te; L = tertiary phosphine ligand) has been investigated. All the complexes have been characterized
by elemental analysis, NMR (1H,31P,77Se,195Pt) spectroscopy and in some cases by X-ray diffraction. The thermal behaviour of these complexes has been studied by TGA.
The pyrolysis of allylpalladium complexes in refluxing xylene yields Pd4E as established by analysis and XRD patterns. 相似文献