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1.
Synthetic procedures are described that allow access to the new complexes cis-[Mo2O5(apc)2], cis-[WO2(apc)2], trans-[UO2(apc)2], [Ru(apc)2(H2O)2], [Ru(PPh3)2(apc)2], [Rh(apc)3], [Rh(PPh3)2(apc)2]ClO4, [M(apc)2], [M(PPh3)2(apc)]Cl, [M(bpy)(apc)]Cl (M(II) = Pd, Pt), [Pd(bpy)(apc)Cl], [Ag(apc)(H2O)2] and [Ir(bpy)(Hapc)2]Cl3, where Hapc, is 3-aminopyrazine-2-carboxylic acid. These complexes were characterized by physico-chemical and spectroscopic techniques. Both Hapc and several of its complexes display significant anticancer activity against Ehrlich ascites tumour cells (EAC) in albino mice.  相似文献   

2.
Co-condensation of atoms of Re, Ru, Rh, Ir and Pt with oxalyl chloride gives metal chloro-carbonyl derivatives which may be used as precursors to the compounds [Re(CO)4Cl]2, [Ru(PMe3)3(CO)Cl2], α-[Ru(CO)3Cl(μ-Cl)]2, [Ru(PPh3)2(CO)2Cl2], [Rh(CO)2(μ-Cl)]2, [Rh(PPh3)2COCl], [Ir(PPh3)(CO)2Cl3] and cis-Pt(CO)2Cl2. Molybdenum atoms with oxalyl chloride give molybdenum-chloro derivatives.  相似文献   

3.
The hydrides [MH(O2CCF3)(CO)(PPh3)2] (M = Ru or Os) react with disubstituted acetylenes PhCCPh and PhCCMe to afford vinylic products [M{C(Ph)CHPh}(O2CCF3)(CO)(PPh3)2] and [M{C(Ph)CHMe}(O2CCF3)(CO) (PPh3)2]/[M{C(Me)CHPh}(O2CCF3)(CO)(PPh3)2] respectively. Acidolysis of these products with trifluoroacetic acid in cold ethanol liberates cis-stilbene and cis-PhHCCHMe respectively thus establishing the cis-stereochemistry of the vinylic ligands. The complexes [M(O2CCF3)2(CO)(PPh3)2] formed during the acidolysis step undergo facile alcoholysis followed by β-elimination of aldehyde to regenerate the parent hydrides [MH(O2CCF3)(CO)(PPh3)2] and thereby complete a catalytic cycle for the transfer hydrogenation of acetylenes. The molecular structure of the methanol-adduct intermediate, [Ru(O2CCF3)2(MeOH)(CO)(PPh3)2] has been determined by X-ray methods and shows that the coordinated methanol is involved in H-bonding with the monodentate trifluoroacetate ligand [MEO-H---OC(O)CF3; O...O = 2.54 Å]. The hydrides [MH(O2CCF3)(CO) (PPh3)2]react with 1,4-diphenylbutadiyne to afford the complexes [M{C(CCPh)CHPh} (O2CCF3)(CO)(PPh3)2]. The ruthenium product, which has also been obtained by treatment of [RuH(O2CCF3)(CO)(PPh3)2] with phenylacetylene, has been shown by X-ray diffraction methods to contain a 1,4-diphenylbut-1-en-3-yn-2-yl ligand. The osmium complexes [Os(O2CCF3)2(CO)(PPh3)2], [OsH(O2CCF3)(CO)(PPh3)2] and [Os{C(CCPh)CHPh}(O2CCF3)(CO)(PPh3)2] all serve as catalysts for the oligomerisation of phenylacetylene. Acetylene reacts with [Ru(O2CCF3)2(CO)(PPh3)2] in ethanol to afford the vinyl complex [Ru(CHCH2)(O2CCF3)(CO)(PPh3)2].  相似文献   

4.
Summary Carbon monoxide reacts with the cationic dinitrosyls [M(NO)2(PPh3)2]+ (M = Rh, Ir) under ambient conditions to produce CO2, N2O and the tricarbonyl cations, (M(CO)3(PPh3)2]+. The cationic tricarbonyls are reconverted into the dinitrosyl reactants on treatment with NO atca. 80°. The Ru(NO)2(PPh3)2 and Os(NO)2(PPh3)2 complexes react similarly with CO but under more vigorous conditions whereas the corresponding dinitrosyls of cobalt and iron do not undergo this reaction under similar conditions. A pentacoordinate dinitrosyl intermediate [M(NO)2(CO)(PPh3)2]n+ is proposed and a mechanism for the catalytic oxidation of CO by NO is presented. Studies of Pt(N2O2)PPh3)2 establish that a dinitrogcn dioxide intermediate, produced by the coupling of two nitrosyl ligands, is reasonable.  相似文献   

5.
Neutral hydrido complexes [ML]ClH(PPh3)3 ([ML] = Ru(CO), Os(CO) and Ir(Cl)] react with thionitrosodimethylamine, Me2NNS, to give [ML]ClH-(SNNMe2)(PPh3)2 with H trans to Me2NNS, while the hydrido cations cis,trans-[[ML]H(SNNMe2)2(PPh3)2]+ are obtained from Me2NNS and [Ru(NCMe)2(CO)-(PPh3)2]+, [OsH(OH2)(CO)(PPh3)3]+ and [IrClH(NCMe)2(PPh3)2]+, respectively. The coordinatively unsaturated aryl complexes [ML′]Cl(p-tolyl)(PPh3)2 ([ML′]Ru(CO), Os(CO) and Os(CS)) coordinate one molecule of Me2NNS to give [ML′]Cl(p-tolyl)(SNNMe2)(PPh3)2, the chloride ligands of which are labile. Spectroscopic data suggest that in all these complexes the Me2NNS ligand adopts a η1(S) coordination mode.  相似文献   

6.
Synthetic procedures are described that allow access to cis-[Mo2O5(cdhp)2]2?, cis-[W2O5(Hcdhp)2], trans-[OsO2(cdhp)2]2?, trans-[UO2(Hcdhp)2], [ReO(PPh3)(Hcdhp)2]X (X =?Cl, I), [ReO2(cdhp)2]?, [M(PPh3)2(cdhp)], [M(bpy)(cdhp)] (M(II) =?Pd, Pt), [Ru(YPh3)2(Hcdhp)2] (Y =?P, As), [Rh(Hcdhp)2Cl(H2O)], [Rh(PPh3)2(Hcdhp)2]ClO4 and [Ir(bpy)(cdhp)Cl2], where Hcdhp, cdhp are the deprotonated monoanion of 5-chloro-3-hydroxypyrid-2-one and dianion of 5-chloro-2,3-dihydroxypyridine, respectively. These complexes were characterized by their Raman, IR, 1H NMR, electronic and mass spectra, conductivity, magnetic and thermal measurements. H2cdhp, cis-K2[Mo2O5(cdhp)2], [Pd(bpy)(cdhp)] display a significant antineoplastic activity against Ehrlich ascites tumor cells (EAC).  相似文献   

7.
Compounds of formula [M(NO)(PPh3)(N4R2)] (I) (M  Rh, Ir; R  SO2? C6H4CH3) have been obtained by the interaction of M(NO)(PPh3)3 with p-toluene-sulphonyl azide in benzene. These new compounds are formulated as tetrazene derivatives on the basis of chemical and spectroscopic data. They react with ligands, L, (e.g. CO, PPh3 to give pentacoordinated species of formula [M(NO)(PPh3(L)(N4R2)].The tetrazene derivatives yield the new nitrosyl compounds, M(NO)(PPh3)Cl2 (II) on treatment with HCl, the nitrogen-containing residue being converted into RN3 and RNH2 species. The compounds (II) are coordinatively unsaturated, and react with ligands L in the same manner as compounds (I), giving new derivatives of formula M(NO)(PPh3)(L)Cl2.IR and NMR spectra of the new compounds are reported and discussed. The presence in solution of a structure in which the chelate tetrazene ring has opened {e.g. [M(NO)(PPh3)(NR)(N3R)]} is suggested by NMR studies.  相似文献   

8.
The complexes (MH(O2CCF3) (CO) (PPh3)2] and (M(O2CCF3)2(CO)(PPh3)2] (M = Ru or Os) react with terminal and internal acetylenes to afford oligomerisation and hydrogenation products, respectively, together with vinylic complexes, including the ruthenium species [Ru(C4HPh2)(O2CCF3)(CO) (PPh3)2], which has been shown by x-ray diffraction methods to contain a 1,4-diphenylbut-1-en-3-yn-2-yl ligand.  相似文献   

9.
Cationic methyl complex of rhodium(III), cis-[Rh(Acac)(PPh3)2(CH3)(Py)][BPh4] (1) as a single isomer with Py in the trans to PPh3 position, is formed upon the reaction of cis-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4] with pyridine in methylene chloride solution.Complex 1 was characterized by elemental analysis and by 31P{1H} and 1H NMR spectra.Cationic pentacoordinate acetyl complexes, trans-[Rh(Acac)(PPh3)2(COCH3)][BPh4] (2) and trans-[Rh(BA)(PPh3)2(COCH3)][BPh4] (3), are prepared by action of carbon monoxide on cis-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4] and cis-[Rh(BA)(PPh3)2(CH3)(CH3CN)][BPh4], respectively, in methylene chloride solutions.Complexes 2 and 3 were characterized by elemental analysis and by IR, 31P{1H}, 13C{1H} and 1H NMR. According to NMR data, 2 and 3 in solution are non-fluxional trigonal bipyramids with β-diketonate and acetyl ligands in the equatorial plane and axial phosphines.In solutions, 2 and 3 gradually isomerize into octahedral methyl carbonyl complexes trans-[Rh(Acac)(PPh3)2(CO)(CH3)][BPh4] (4) and trans-[Rh(BA)(PPh3)2(CO)(CH3)][BPh4] (5), respectively.Complexes 4 and 5 were characterized by IR, 31P{1H}, 13C{1H} and 1H NMR, without isolation.Upon the action of PPh3 on cis-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4] and cis-[Rh(BA)(PPh3)2(CH3)(CH3CN)] [BPh4], reductive elimination of the methyl ligand as a phosphonium salt, [CH3PPh3][BPh4], occurs to give square planar rhodium(I) complexes [Rh(Acac)(PPh3)2] and[Rh(BA)(PPh3)2], respectively. The reaction products were identified in the reaction mixtures by 31P{1H} and 1H NMR.  相似文献   

10.
Summary The reaction of previously reported RhI and IrI cationic complexes towards carbon monoxide and triphenylphosphine has been studied. Carbonyl rhodium(I) mixed complexes of the formulae [Rh(CO)L2(PPh3)]ClO4, (L=tetrahydrothiophene(tht), trimethylene sulfide(tms), SMe2, or SEt2), [(CO)(PPh3)Rh{-(L-L)}2Rh(PPh3)(CO)](ClO4)2 (L-L= 2,2,7,7-tetramethyl-3,6-dithiaoctane (tmdto), (MeS)2(CH2)3 (dth), or 1,4-dithiacyclohexane (dt), [Rh(CO)L(PPh3)2]ClO4 (L= tht, tms, SMe2, or SEt2), and carbonyl iridium(I) complexes of the formulae [Ir(CO)2(COD)(PPh3)]ClO4, [Ir(CO)(COD)(PPh3)2]ClO4, [(CO)(COD)(PPh3) Ir{-(L-L)} Ir(PPh3)(COD)(CO)](ClO4)2 (L-L = tmdto or dt), [(CO)2 (PPh3)Ir(-tmdto)Ir(PPh3)(CO)2](ClO4)2, [(CO)2(PPh3) Ir(-dt)2Ir(PPh3)(CO)2](ClO4)2, were prepared by different synthetic methods.  相似文献   

11.
《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   

12.
Perfluoronorbornadiene reacts with the compounds [M(PPh3)4] (M = Pt, Pd) and [IrCl(CO)(PMePh2)2] to give the adducts [(C7F8)M(PPh3)2] and [(C7F8)IrCl(CO)(PMePh2)2] in which one of the double bonds is coordinated to the metal atom. The platinum complex reacts further with [Pt(PPh3)4] to give [(C7F8){Pt(PPh3)2}2] having both double bonds coordinated to a Pt atom. The carbonylmetal anions [M?] react to form the mono-substitution products [(C7F7)M] (M = Mn(CO)5, Re(CO)5, Ir(CO)2(PPh3)2, Rh(CO)2(PPh3)2), but the use of an excess of [Fe(CO)2(η-C5H6)]? leads to substitution of one fluorine atom on each of the double bonds. The complex having M = Mn(CO)5 reacts with [Pt(PPh3)4] to afford the derivative [(C7F7){Mn(CO)4(PPh3)}{Pt(PPh3)2}], and the compound where M = Ir(CO)2(PPh3)2 undergoes an oxidative addition reaction with acetyl chloride. Oxidative coupling products have been isolated on UV irradiation of a mixture of perfluoronorbornadiene and [Fe(η4-CH2CRCHCH2)(CO)3] (R = H, Me), and under similar conditions the reaction with Fe(CO)5 affords [(C7F8)Fe(CO)4] in very low yield.  相似文献   

13.
Thiocyanogen and selenocyanogen react with Ru(CO)3(PPh3)2 to give respectively the complexes Ru(CO)2(PPh3)2(NCS)2 and Ru(CO)2(PPh3)2(NCSe)2. (M—NCS and M—SCN represent N- and S-thiocyanato groups, M—NCSe and M—SeCN represent N- and Se-selenocyanato groups respectively, while M—CNS indicates the bridging coordination mode of thiocyanate.) Only the thiocyanogen reacts with Ru3(CO)12 giving [Ru(CO)2(CNS)2]n, which dissolves in hot coordinating solvents, such as pyridine, to form Ru(CO)2(py)2(NCS)2. Selenocyanogen is less effective than thiocyanogen in the oxidative addition reactions with rhodium(I) and iridium(I) complexes; in fact selenocyanogen does not react with Rh(CO)(PPh3)2Cl while with Ir(CO)(PPh3)2Cl the former gives Ir(CO)(PPh3)2(SeCN)2Cl by an equilibrium reaction. The coordination number of the metal and the charge on the complex do not change the bonding mode of the thiocyanate and selenocyanate groups in the iridium(III) complexes; in the Ir(PPh3)2ClX2 and [Ir(Ph2PC2H4PPh2)2X2]+ (X = SCN and SeCN) complexes the pseudohalogens are S- and Se-bonded.The complexes trans-M(PPh3)2(SeCN)2 (M = Pd, Pt) have been obtained by reacting M(PPh3)4 with selenocyanogen.  相似文献   

14.
1,2,3,4,7,7-Hexafluorobicyclo[2.2.1]heptadiene (1) and 2,3-bis(trimethyltin)-1,4,5,6,7,7-hexafluorobicyclo[2.2.1]hepta-2,5-diene (2) react with [M(Ph3P)4] (M = Pt, Pd) to afford air-stable adducts. 2,3-Dichloro-1,4,5,6,7,7-hexafluorobicyclo[2.2.1]hepta-2,5-diene (3) gives only [PtCl2(PPh3)2] with [Pt(Ph3P)4], but a low yield of an adduct was obtained with [Pd(PPh3)4]. The diene 1 also reacts with Fe(CO)5 to form the complex [(C7H2F6)Fe(CO)4], and with [Rh(C2H4)2(acac)] to give [(C7H2F6)Rh(acac)] in which the diene acts as a bidentate ligand. Similar products could not be isolated from the reactions of 2 and 3. A stable adduct, believed to be [{C7F6(SnMe3)2}Rh(CO)2(μ-Cl)2Rh(CO)2] has been isolated from the reaction between 2 and [Rh(CO)2Cl]2. This adduct reacts with PPh3 to give the bridge-cleavage product [{C7F6(SnMe3)2}RhCl(CO)(PPh3)2]. Reaction of 1 with [Rh(CO)2Cl]2 gives an unstable adduct which could not be isolated, and 2 does not react at room temperature. The chloro derivative 3 reacts with [PdCl2(PhCN)2] to give the adduct [(C7F6Cl2)PdCl(PhCN)], but 1 and 2 do not react under similar conditions. Stable substitution products [(C7F6R2)M] (R = H, M = Fe(CO)2(η-C5H5); R = SnMe3, M = Fe(CO)2(η-C5H5), Mn(CO)5, Ir(CO)2(PPh3)2, Rh(CO)2(PPh3)2; R = Cl, M = Ir(CO)2(PPh3)2, Rh(CO)2(PPh3)2) have been isolated from the reactions of the dienes with carbonylmetal anions. Insertion of the CHCH bond occurs when 1 is heated with [MnMe(CO)5] to give [{C7F6H2C(O)Me}Mn(CO)4], and this, on reaction with either PPh3 or [Pt(PPh3)4], gives [(C7F6H2COMe)Mn(CO)4PPh3].  相似文献   

15.
The O-perrhenato complexes LnMOReO3 (LnM = Re(CO)5, Rh(PPh3)2(CO), Ir(PPh3)2(CO), Pt(PPh3)2(H), Ru(η5-C5H5)(PPh3)2, Os(PPh3)3(CO)(H), Ir(PPh3)2(CO)(H)(Cl) have been prepared from the corresponding halogeno compounds with AgReO4 or NaReO4, respectively. The spectroscopic data (IR, 1H NMR) indicate that ReO4− is a stronger ligand compared to ClO4−, SO3CF3− and BF4−.  相似文献   

16.
Treatment of a THF solution of trans-[ReCl(N2)(dppe)2] (dppe = Ph2PCH2CH2PPh2) with NO, in the presence of Tl[BF4], forms trans-[Re(NO)2(dppe)2][BF4], a rare formal 20-electron d8-rhenium nitrosyl complex which, by reaction with HX (X = BF4, Cl or HSO4), gives trans-[ReF(NO)(dppe)2][BF4] (2) (the X-ray structure of which is reported) or trans-[ReX(NO)(dppe)2]X (3, X = Cl or HSO4), respectively, as well as nitrous oxide.  相似文献   

17.
《Polyhedron》1987,6(11):2009-2018
A new bidentate ligand {2-(diphenylphosphino)ethyl}benzylamine(DPEBA) was synthesized and characterized based on the IR, mass and 1H, 13C and 31P NMR spectra. Various complexes of platinum group metal ions and Ni(II) and Co(II) ions with the ligand were synthesized. Reaction of RuCl2(PPh3)3 or RuCl2(Me2SO)4 with the ligand DPEBA, resulted in formation of a penta-coordinate, Ru(II) species of the composition [RuCl(DPEBA)2]Cl. Carbonylation of [RuCl(DPEBA)2]Cl gave an octahedral carbonyl complex of the type [RuCl(CO)(DPEBA)2]Cl. The reaction of RuCl3·3H2O or RuCl3(AsPh3)2MeOH with a twofold excess of the ligand gave an octahedral Ru(III) cationic species [Ru(DPEBA)2Cl2]Cl. Carbonylation of the Ru(III) complex gave rise to a carbonyl complex [RuCl(CO)(DPEBA)2]Cl2. The ligand DPEBA reacts with cobalt(II) chloride in methanol to give the 1 : 1 complex [Co(DPEBA)Cl2]. A series of Rh(I) complexes [Rh(DPEBA)2Cl], [ RhCl(CO)(DPEBA)] and [Rh(DPEBA)2]Cl were synthesized by the reaction of DPEBA with RhCl(PPh3)3, RhCl(CO)(PPh3)2 and [Rh(COD)Cl]2, respectively. Reaction of [Ir(COD)Cl]2 and IrCl(CO)(PPh3)2 with the ligand DPEBA, gave the square-planar complexes [Ir(DPBA)2]Cl and [Ir(DPEBA)(CO)Cl], respectively. Octahedral cationic complexes of the type [M(DPEBA)2Cl2]Cl (M = Rh(III), Ir(III)) were synthesized by the reaction of the ligand DPEBA and rhodium and iridium trichlorides. Reaction of NiCl2·6H2O with DPEBA in 1 : 2 molar equivalents, in boiling butanol gave an octahedral neutral complex [Ni(DPEBA)2Cl2] which readily rearranges to the square-planar complex [Ni(DPEBA)2]Cl2 in methanol. Reaction of Pd(II) and Pt(II) chlorides with DPEBA gave square-planar, cationic complexes of the type [M(DPEBA)2Cl]Cl (M = Pd, Pt). All the complexes were characterized on the basis of their analytical and spectral data.  相似文献   

18.
Salicylaldehyde thiosemicarbazone (H2saltsc) reacts with [M(PPh3)3X2] (M = Ru, Os; X = Cl, Br) to afford complexes of type [M(PPh3)2(Hsaltsc)2], in which the salicylaldehyde thiosemicarbazone ligand is coordinated to the metal as a bidentate N,S-donor forming a four-membered chelate ring. Reaction of benzaldehyde thiosemicarbazones (Hbztsc-R) with [M(PPh3)3X2] also affords complexes of similar type, viz. [M(PPh3)2(bztsc-R)2], in which the benzaldehyde thiosemicarbazones have also been found to coordinate the metal as a bidentate N,S-donor forming a four-membered chelate ring as before. Reaction of the Hbztsc-R ligands has also been carried out with [M(bpy)2X2] (M = Ru, Os; X = Cl, Br), which has afforded complexes of type [M(bpy)2(bztsc-R)]+, which have been isolated as perchlorate salts. Coordination mode of bztsc-R has been found to be the same as before. Structure of the Hbztsc-OMe ligand has been determined and some molecular modelling studies have been carried out determine the reason for the observed mode of coordination. Reaction of acetone thiosemicarbazone (Hactsc) has then been carried out with [M(bpy)2X2] to afford the [M(bpy)2(actsc)]ClO4 complexes, in which the actsc ligand coordinates the metal as a bidentate N,S-donorformingafive-membered chelate ring. Reaction of H2saltsc has been carried out with [Ru(bpy)2Cl2] to prepare the [Ru(bpy)2(Hsaltsc)]ClO4 complex, which has then been reacted with one equivalent of nickel perchlorate to afford an octanuclear complex of type [Ru(bpy)2(saltsc-H)4Ni4](ClO4)4.  相似文献   

19.
Dinuclear rhodium complexes of the type [Rh2(C2O4)(diolefin)2] (diolefin)2  1,5-cyclooctadiene, 2,5-norbornadiene and tetrafluorobenzobarrelene) with bridging oxalate ligands have been obtained by reaction of [Rh(acac)(diolefin)] with oxalic acid (2: 1 mol ratio). The use of a 1 : 1 molar ratio affords [Rh(HC2O4)(COD)], that reacts with [Ir(acac)(COD)] yielding the heterodinuclear [(COD)Rh(C2O4)Ir(COD)] complex. Treatment of [Rh2(C2O4)(diolefin)2] complexes with phenanthroline type ligands leads to ionic complexes of formula [Rh(diolefin) (phen)][Rh(C2O4)(diolefin)]. Bubbling of carbon monoxide through solutions of the diolefin complexes leads to the formation of carbonylrhodium species of formula [Rh2(C2O4)(CO)2L2] (L = CO, PPh3t-BuNC) or [Rh(CO)2(phen)] - [Rh(C2O4)(CO)2]. Other related malonate complexes are also described.  相似文献   

20.
Summary Reactions of cinnamonitrile (trans-PhCH=CHCN) with [M(ClO4)(CO)(PPh3)2] (M=Rh or Ir) produce hydrogenation oftrans-PhCH=CHCN to PhCH2CH2CN at 100°C under 3 atm of hydrogen.  相似文献   

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