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1.
The trivalent ruthenium, rhodium and iridium complexes of dipicolinic acid and its mixed ligand complexes with several nitrogen, oxygen donor molecules, of types: Na[M(dipic)2]·2H2O and [M(dipic)(N-O)]·nH2O (where M = Ru(III), Rh(III) or Ir(III); dipicH2 = dipicolinic acid; NOH represents different nitrogen, oxygen donor molecules, viz., picolinic acid, nicotinic acid, isonicotinic acid, glycine, aminophenol, o- or p-aminobenzoic acid), have been synthesized and characterised on the basis of elemental analyses, electrical conductance, magnetic susceptibility measurements and spectral (electronic and infrared) data. The parent dipicolinic acid complexes are found to have a six-coordinate pseudooctahedral structure, whereas for mixed ligand complexes, a polymeric six-coordinate structure has been assigned. Various ligand field and nephelauxetic parameters have also been evaluated. 相似文献
2.
The synthesis and characterization of palladium(II) and platinum(II) complexes of isomeric bidentate 2-pyridyl-1,2,3-triazole “click” ligands is reported. The complexes have been fully characterized by elemental analysis, HRESI-MS, IR, UV–Vis, 1H and 13C NMR spectroscopy. Additionally, the molecular structures of the Pd(II) and Pt(II) complexes of the 2-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]pyridine ligand are confirmed by X-ray crystallography. Solution studies indicate the 2-(1-benzyl-1H-1,2,3-triazol-4-yl)pyridine ligand forms more stable complexes with Pd(II) and Pt(II) than the isomeric 2-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]pyridine ligand. 相似文献
3.
2,2′-Bis(o-diphenylphosphino)bibenzyl, o-Ph2PC6H4CH2CH2C6H4PPh2-o (bdpbz), is dehydrogenated by various rhodium complexes to give the planar rhodium(I) complex
, from which the ligand, 2,2′-bis(o-diphenylphosphino)-trans-stilbene (bdpps) can be displaced by treatment with sodium cyanide. The stilbene forms stable chelate olefin complexes with planar rhodium(I) and iridium(I) and with octahedral iridium(III). On reaction with halide complexes of nickel(II), palladium(II) or platinum(II), the stilbene ligands
(R = Ph or o-CH3C6H4) lose a vinyl proton in the form of hydrogen chloride to give chelate, planar σ-vinyls of general formula
=CHC6H4PR2-o) (M = Ni, Pd, Pt; X = Cl, Br, I) of high thermal stability; analogous methyl derivatives
=CHC6H4PR2-o) are obtained from Pt(CH3)2(COD) (COD = 1,5-cyclooctadiene) and the stilbene ligands. The bibenzyl also forms chelate σ-benzyls
HCH2C6H4PPh2-o) (M = Pd, Pt; X = Cl, Br, I). The 1H NMR spectra of the o-tolyl methyl groups in the compounds
=CHC6H4PR2-o) (M = Ni, Pd, Pt; R = o-CH3C6H4) vary with temperature, probably as a consequence of interconversion of enantiomers arising from restricted rotation about the M---P and M---C bonds. Possible mechanisms for the dehydrogenation reactions are briefly discussed. 相似文献
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4.
Summary Some thiazolidine-2-thione and thiomorpholin-3-one complexes of rhodium(lll), iridium(III), ruthenium(III) and osmium(III) have been prepared and characterized by chemical analysis, conductivity measurements, room temperature magnetic moment studies, electronic, i.r. and far i.r. spectra and n.m.r. measurements. From the magnetic properties it was concluded that the above ligands form low-spin complexes with all the metal ions. The position and multiplicity of the metal-halogen stretching modes in the far-i.r. region have been extensively investigated and discussed; the results are particularly useful in distinguishing between themer- andfac-isomers in the octahedral compounds of the ML3 X3 type. The wavelengths of the principal electronic absorption peaks have been accounted for quantitatively in terms of the crystal field theory and the various parameters have been calculated. On the basis of the electronic spectra a trigonal bipyramidal geometry,D
3h, has been established for the Ru(tm)2Cl3 complex; the Ir(rm)2Cl3 · H2O complex has also been prepared. It is penta-coordinated and a trigonal bipyramidal environment is suggested for the iridium(III) ion. 相似文献
5.
Summary Rhodium(I), iridium(I), palladium(II) and platinum(II) complexes of the phosphinoamide ligands, Ph2PCH2CONHR (R = H, HDPA; Me, MDPA; Ph, PDPA) were prepared and characterized by using conductivity data, i.r., 1H and 31P(H) n.m.r. spectral data. Reaction of the ligands with MCl(PPh3)3 and MCl(CO)(PPh3)2 (M = Rh, Ir) in CH2Cl2 under reflux lead to the formation of MCl(PPh3)2 [Ph2PCH2C(O)NHR] and MCl(CO)(PPh3)[Ph2PCH2–C(O)HNR] respectively. The reaction of either K2MCl4 or cis-MCl2(PPh3)2 affords complexes of the type cis-MCl2[Ph2PCH2C(O)NHR]2 (M = Pd, Pt). A similar product results even from the reaction of phosphinoamides with cis-platin. Possible structures are proposed for the complexes based on their physicochemical data 相似文献
6.
《Polyhedron》1988,7(5):417-418
The synthesis and characterization of the platinum metal—1,3-diaryltriazenido complexes [Ru(ArNNNAr)(CO)3]2, [Ru(ArNNNAr)2]2, cis-Ru(ArNNNAr)2(CO)2, MX2(ArNNNAr)(PPh3)2 (M = Ru, Os; X = Cl, Br) and M′(ArNNNAr)3 (M′= Ru, Os, Rh and Ir) are reported. Axial ligand substitution in [Ru(ArNNNAr)(CO)3]2 and adduct formation by [Ru(ArNNNAr)2]2 are described. In contrast to other known Ru(II)/Ru(II) “lantern” molecules, the species [Ru(ArNNNAr)2]2 have measured magnetic moments equivalent to ca one unpaired electron per dimer, which are presumably due to population of the spin states σ2π4δ2π*4 and σ2π4δ2π*3σ*1. 相似文献
7.
Summary New complexes of the general formula M(L)3Cl3 and M(5-AInz)2Cl3 · n H2O (where M = RuIII, RhIII and IrIII; L = indazole and 5-nitroindazole; n=1–2) have been synthesized and characterised by elemental analysis, molar conductance, magnetic susceptibility and i.r. and electronic spectral measurements. All the complexes are covalent and apparently have an octahedral geometry. The ligands are monocoordinated through the pyrrole nitrogen. From the far i.r. spectra amer configuration has been assigned to the indazole and 5-nitroindazole complexes. 相似文献
8.
F.R. Hartley 《Journal of organometallic chemistry》1981,216(2):277-279
It is shown that trigonal bipyramidal platinum(II), rhodium(I) and iridium(I) olefin complexes are better classified with the platinum(O) complex [Pt(PPh3)2(C2H4)] as class T olefin complexes than with the square-planar platinum(II) complexes such as [Pt(C2H4)Cl3]- which fall in class S. The underlying reasons for this are considered to be electronic rather than steric as was previously suggested. 相似文献
9.
Twelve new copper(II) complexes in which N,N′-bis-(2-pyridylmethyl)-oxamidatocopper(II) or N,N′-bis(2-pyridylethyl)-oxamidatocopper(II) coordinates as a bidentate ligand have been isolated and characterized. These complexes have a structure bridged by the oxamide group (including two tetranuclear complexes formed by olation of two binuclear complexes, of. Fig. 1), and possess Cu? Cu interaction resulting in a sub-normal magnetic moment at room temperature. In one of them, [Cu2(PMoxd) (bipy)2] (NO3)2 (cf. Fig. 2), each copper(II) ion has a five-coordinated environment. 相似文献
10.
Reactions of [Cp*M(μ-Cl)Cl]2 (M = Ir, Rh; Cp* = η5-pentamethylcyclopentadienyl) with bi- or tri-dentate organochalcogen ligands Mbit (L1), Mbpit (L2), Mbbit (L3) and [TmMe]− (L4) (Mbit = 1,1′-methylenebis(3-methyl-imidazole-2-thione); Mbpit = 1,1′-methylene bis (3-iso-propyl-imidazole-2-thione), Mbbit = 1,1′-methylene bis (3-tert-butyl-imidazole-2-thione)) and [TmMe]− (TmMe = tris (2-mercapto-1-methylimidazolyl) borate) result in the formation of the 18-electron half-sandwich complexes [Cp*M(Mbit)Cl]Cl (M = Ir, 1a; M = Rh, 1b), [Cp*M(Mbpit)Cl]Cl (M = Ir, 2a; M = Rh, 2b), [Cp*M(Mbbit)Cl]Cl (M = Ir, 3a; M = Rh, 3b) and [Cp*M(TmMe)]Cl (M = Ir, 4a; M = Rh, 4b), respectively. All complexes have been characterized by elemental analysis, NMR and IR spectra. The molecular structures of 1a, 2b and 4a have been determined by X-ray crystallography. 相似文献
11.
Annibale Giuliano Marangoni Giampaolo Pitteri Bruno Visentin Fabiano Bobbo Tatiana 《Transition Metal Chemistry》2000,25(4):485-489
The reactions of AuIII, PtII and PdII complexes with 2-pyridinecarboxaldehyde (2CHO-py) have been examined in protic (H2O, MeOH, EtOH) and aprotic (DMF, CH2Cl2) solvents. Compounds in which the pyridine ligand is N-coordinated, either in the original aldehydic form or in a new form
derived from addition of one or two protic molecules, have been isolated, namely: [Au(2CHO-py · H2O)Cl3], [Au(2CHO-py · MeOH)Cl3], [Au(2CHO-py · 2EtOH)Cl3], cis-[Pt(2CHO-py)2Cl2], trans-[Pd(2CHO-py)2Cl2], trans-[Pt(dmso)(2CHO-py)Cl2], [Pt{C5H4N-(CH2SMe)}Cl(2CHO-py)](ClO4), [Pt(terpy)(2CHOpy)](ClO4)2, [Pt(terpy)(2CHO-py · H2O)](ClO4)2 (terpy = 2,2′:6′,2′′-terpyridine). 1H-n.m.r. experiments show that the addition of the protic molecule(s) to the PtII and PdII complexes is reversible. The effects of the nature of the metal ion and the ancillary ligands as well as of the total charge
of the complexes on the relative stability of the addition products are discussed.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
12.
Summary 2,6-Dimethyl-4H-pyran-4-thione (DMTP) acts as a sulphur donor towards PtII and PdII halides yielding adducts of general formula [M(DMTP)2X2] (M=Pd or Pt; X=Cl, Br or I). When complex syntheses are performed in benzene, the solvated species [M(DMTP)2X2]·C6H6 (M=Pd or Pt; X=Cl or Br) are obtained. The compounds have been characterized by i.r. and n.m.r. (1H and13C) spectroscopy and by thermogravimetric data. The adduct geometry and the influence of benzene are discussed. 相似文献
13.
Summary Complexes of 2-mercapto-1-methylimidazole (TMZ) with PtII, PdII, RhIII and RuIII of the general formulae Pt(TMZ)2Cl2, Pd(TMZ)4Cl2. Rh(TMZ)Cl3 and Ru(TMZ)Cl3 have been obtained. The thermal stabilities of the compounds were estimated by derivatographic measurements and the electron-donating atom of the measurements and the electron-donating atom of the ligand was identified from the i.r. absorbtion spectra. Lattice constants for the PtII and PdII complexes were estimated from their x-ray powder diffraction patterns. 相似文献
14.
Goran N. Kaluđerović Esther Hernández-Corroto Wolfgang Brandt Bojana B. Zmejkovski Santiago Gómez-Ruiz 《Journal of Coordination Chemistry》2016,69(8):1337-1345
Four palladium(II) complexes with R2edda ligands, dichlorido(O,O′-dialkylethylenediamine-N,N′-diacetate)palladium(II) monohydrates, [PdCl2(R2edda)]?H2O, R = Me, Et, n-Pr, i-Bu, and the new ligand precursor i-Bu2edda?2HCl?H2O, O,O′-diisobutylethylenediamine-N,N′-diacetate dihydrochloride monohydrate, were synthesized and characterized by IR, 1H and 13C NMR spectroscopy, and elemental analysis. DFT calculations were performed for the palladium(II) complexes and a high possibility for isomer formation due to stereogenic N ligand atoms was confirmed. Moreover, DFT simulations revealed energetic profile of isomer formation. Computational outcomes are in agreement with spectroscopic instrumental findings, both strongly indicating a non-stereoselective reaction between selected esters and K2[PdCl4], forming isomers. 相似文献
15.
3,3′-Dicarbomethoxy-2,2′-bipyridyl(DCMB)reacts with K2MCl4(M = Pd,Pt) to give M(DCMB)Cl2 and with RhCl3 to give the cis-[Rh(DCMB)2Cl2]+ ion. Attempts to prepare the tris (DCMB) complex with Rh(III) and analogous Co(III) complexes were unsuccessful. 相似文献
16.
Yasuhiro Yamamoto Hideki Nakamura Jian-Fang Ma 《Journal of organometallic chemistry》2001,640(1-2):10-20
Reactions of [(η6-arene)RuCl2]2 (1) (η6-arene=p-cymene (1a), 1,3,5-Me3C6H3 (1b), 1,2,3-Me3C6H3 (1c) 1,2,3,4-Me4C6H2(1d), 1,2,3,5-Me4C6H2 (1e) and C6Me6 (1f)) or [Cp*MCl2]2 (M=Rh (2), Ir (3); Cp*=C5Me5) with 4-isocyanoazobenzene (RNC) and 4,4′-diisocyanoazobenzene (CN–R–NC) gave mononuclear and dinuclear complexes, [(η6-arene)Ru(CNC6H4N=NC6H5)Cl2] (4a–f), [Cp*M(CNC6H4N=NC6H5)Cl2] (5: M=Rh; 6: M=Ir), [{(η6-arene)RuCl2}2{μ-CNC6H4N=NC6H4NC}] (8a–f) and [(Cp*MCl2)2(μ-CNC6H4N=NC6H4NC)}] (9: M=Rh; 10: M=Ir), respectively. It was confirmed by X-ray analyses of 4a and 5 that these complexes have trans-forms for the ---N=N--- moieties. Reaction of [Cp*Rh(dppf)(MeCN)](PF6)2 (dppf=1,1′-bis (diphenylphosphino)ferrocene) with 4-isocyanoazobenzene gave [Cp*Rh(dppf)(CNC6H4N=NC6H5)](PF6)2 (7), confirmed by X-ray analysis. Complex 8b reacted with Ag(CF3SO3), giving a rectangular tetranuclear complex 11b, [{(η6-1,3,5-Me3C6H3)Ru(μ-Cl}4(μ-CNC6H4N=NC6H4NC)2](CF3SO3)4 bridged by four Cl atoms and two μ-diisocyanoazobenzene ligands. Photochemical reactions of the ruthenium complexes (4 and 8) led to the decomposition of the complexes, whereas those of 5, 7, 9 and 10 underwent a trans-to-cis isomerization. In the electrochemical reactions the reductive waves about −1.50 V for 4 and −1.44 V for 8 are due to the reduction of azo group, [---N=N---]→[---N=N---]2−. The irreversible oxidative waves at ca. 0.87 V for the 4 and at ca. 0.85 V for 8 came from the oxidation of Ru(II)→Ru(III). 相似文献
17.
Ní Dhubhghaill OM Lennon J Drew MG 《Dalton transactions (Cambridge, England : 2003)》2005,(19):3213-3220
The previously synthesised Schiff-base ligands 2-(2-Ph(2)PC(6)H(4)N[double bond, length as m-dash]CH)-R'-C(6)H(3)OH (R'= 3-OCH(3), HL(1); 5-OCH(3), HL(2); 5-Br, HL(3); 5-Cl, HL(4)) were prepared by a faster, more efficient route involving a microwave assisted co-condensation of 2-(diphenylphosphino)aniline with the appropriate substituted salicylaldehyde. HL(1-4) react directly with M(II)Cl(2)(M = Pd, Pt) or Pt(II)I(2)(cod) affording neutral square-planar complexes of general formula [M(II)Cl(eta(3)-L(1-4))](M = Pd, Pt, 1-8) and [Pt(II)I(eta(3)-L(1-4))](M = Pd, Pt, 9-12). Reaction of complexes 1-4 with the triarylphosphines PR(3)(R = Ph, p-tolyl) gave the novel ionic complexes [Pd(II)(PR(3))(eta(3)-L(1-4))]ClO(4)(13-20). Substituted platinum complexes of the type [Pt(II)(PR(3))(eta(3)-L(1-4))]ClO(4)(R = P(CH(2)CH(2)CN)(3)21-24) and [Pt(II)(P(p-tolyl)(3))(eta(3)-L(3,4))]ClO(4)( 25 and 26 ) were synthesised from the appropriate [Pt(II)Cl(eta(3)-L(1-4))] complex (5-8) and PR(3). The complexes are characterised by microanalytical and spectroscopic techniques. The crystal structures of 3, 6, 10, 15, 20 and 26 were determined and revealed the metal to be in a square-planar four-coordinate environment containing a planar tridentate ligand with an O,N,P donor set together with one further atom which is trans to the central nitrogen atom. 相似文献
18.
Song YH Chiu YC Chi Y Cheng YM Lai CH Chou PT Wong KT Tsai MH Wu CC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(18):5423-5434
A series of blue phosphorescent iridium(III) complexes 1-4 with nonconjugated N-benzylpyrazole ligands were synthesized and their structural, electrochemical, and photophysical properties were investigated. Complexes 1-4 exhibit phosphorescence with yields of 5-45 % in degassed CH2Cl2. Of the compounds, 1 showed emission that was nearly true blue at 460 nm with a lack of vibronic progression. These photophysical data clearly demonstrate that the methylene spacer of the cyclometalated N-benzylpyrazole chelate effectively interrupts the pi conjugation upon reacting with a third L X chelating chromophore. This gives a feasible synthesis for the blue phosphorescent complexes with a sufficiently large energy gap. In another approach, these complexes were investigated for their suitability for the host material in phosphorescent OLEDs. The device was synthesized by using 1 as the host for the green-emitting [Ir(ppy)3] dopant, which exhibits an external quantum conversion efficiency (EQE) of up to 11.4 % photons per electron (and 36.6 cdA(-1)), with 1931 Commission Internationale de L'Eclairage (CIE) coordinates of (0.30, 0.59), a peak power efficiency of 21.7 lmW(-1), and a maximum brightness of 32000 cdm(-2) at 14.5 V. At the practical brightness of 100 cdm(-2), the efficiency remains above 11 % and 18 lmW(-1), demonstrating its great potential as the host material for phosphorescent organic light-emitting diodes. 相似文献
19.
Summary As an approach to systems containing methionine residues, 3-acetyl-4-hydroxy-6-methyl-2H-pyran-2-one (HDh, dehydroacetic acid) was treated with L-methionine (MetH) or L-methionine methylester (MetM). By condensation at the acyl group and transfer of the phenolic hydrogen on the nitrogen atom, the related ligands DhMetH and DhMetM, were isolated, and form complexes of formula [MX2(L)2](M = Pd or Pt, L = DhMetM, X = Cl, Br or I; L = DhMetH, X = Cl or Br) and [MI2(DhMetH)] with palladium and platinum dihalides. The reaction of the DhMetK carboxylate with MCl2 in various media is discussed. Ligands and complexes were characterized by i.r. and n.m.r. (1H and13C) spectroscopy and, in some cases, by thermogravimetric measurements. The ligands behave as monodentate sulphur donors, the 12 complexes showing atrans geometry except for [PtCl2(DhMetH)2], which is probably a mixture ofcis andtrans isomers. 相似文献
20.
Matsuo Nonoyama 《Transition Metal Chemistry》1990,15(5):366-370
Summary
N, N-Dimethyl-3-furancarbothioamide (Hbft) was cyclometallated with Li2PdCl4, K2PtCl4, RuCl2(CO)3, and RhCl (PBu3)2 (PBu3=tri-n-butylphosphine) to give, respectively, PdCl(bft), PtCl(bft), RuCl(bft)(CO)2, and RhCl2 (bft)(PBu3)2. These and some of their derivatives were characterized spectroscopically. Cyclometallation occurs regioselectively at position 2 of the furan ring to give a five-membered metallaheterocycle, along with Secoordination of the thioamide group. When the position 2 of the furan ring is blocked by a methyl group,N, N-dimethyl-2-methyl-3-furancarbothioamide (Hmft) is, in similar conditions, cyclopalladated at the N–Me substituout of the thioamide group, the furan ring being left intact. Position 4 of the furan ring of both Hbft and Hmft is unreactive toward cyclometallation. 相似文献