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
Summary The synthesis and characterisation of products obtained by the interaction between [Ir(NO)(MeCN)2(PPh3)2]2+ and 2-aminophenol derivatives are reported. Tetracoordinate d8complexes of the type Ir(NO)(2-ap)(PPh3) and pentacoordinate d complexes6of the type [Ir(2-ap)(PPh3)3]+ where 2-ap=2-aminophenol, 2-amino-4-nitrophenol, 2-amino-5-methylphenol, 2-3-aminonaphthol and 2-amino-4-methylphenol are obtained. The Ir(NO)(PPh3)3 complex is always present as a byproduct. Physical properties, i.r. spectra and conductivity data of the complexes are tabulated. Reaction schemes for the formation of the three complexes are proposed and discussed. 相似文献
The reactions of [Ru(H)(Cl)(CO)(PPh3)3] with 3,5-di-tert-butyl-o-benzoquinone (dbq) and 3,4,5,6-tetrachloro-o-benzoquinone (tcq) have afforded the corresponding semiquinone complexes [RuII(dbsq)(Cl)(CO)(PPh3)2] and [RuII(tcsq)(Cl)(CO)(PPh3)2], respectively. The reaction of [Ru(H)2(CO)(PPh3)3] with tcq has furnished [RuII(tcsq)(H)(CO)(PPh3)2]. Structure determination of [Ru(dbsq)(Cl)(CO)(PPh3)2] has revealed that it is a model semiquinonoid chelate with two equal C---O lengths ( 1.291(6) and 1.296(6) Å). The complexes are one-electron paramagnetic (1.85μB) and their EPR spectra in fluid media display a triplet structure (g2.00) due to superhyperfine coupling with two trans-31P atoms (Aiso17 G). The stretching frequency of the CO ligand increases by 20 cm−1 in going from [Ru(dbsq)(Cl)(CO)(PPh3)2] to [Ru(tcsq)(Cl)(CO)(PPh3)2] consistent with electron withdrawal by chloro substituents. For the same reason the E1/2 values of the cyclic voltammetric quinone/semiquinone and semiquinone/catechol couples undergo a shift of 500 mV to higher potentials between [Ru(dbsq)(Cl)(CO)(PPh3)2] and [Ru(tcsq)(Cl)(CO)(PPh3)2]. 相似文献
Two pseudohalide hydride carbonyl ruthenium(II) complexes with formulae: [RuH(N3)(CO)(PPh3)3] (1) and [RuH(NCO)(CO)(PPh3)3] (2) have been synthesized by the reactions of [RuHCl(CO)(PPh3)3] with sodium azide or sodium cyanate, respectively, and are compared with the previously described thiocyanate analog [RuH(NCS)(CO)(PPh3)3]. The molecular structures of the new compounds were determined by X-ray crystallography and their spectroscopic properties have been studied. Based on the crystal structures, computational investigations have been carried out in order to determine the electronic structures of the complexes. The electronic spectra were calculated with the use of time-dependent DFT methods, and the electronic spectra of the transitions were correlated with the molecular orbitals of the complexes. 相似文献
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
The hydrido-thiocarbonyl osmium(II) complexes OsH2(CS)(PPh3)3, OsHCl(CS)(PPh3)3, OsH(OClO3)(CS)(PPh3)3, OsHCl(CS)(CNR)(PPh3)2 and [OsH(CS)(CO)(PPh3)3]+, (R = p-tolyl), have been derived from OsCl2(CS)(PPh3)3 and [OsH(CS)(CO)(PPh3)3]+, the latter can be deprotonated to give the zerolavent complex, Os(CS)(CO)(PPh3)3. 相似文献
ortho-Substituted aryliridium(I) complexes of the type [Ir(RnC6H5-n)(CO)L2] (RnC6H5-n = 2-EtC6H4; 2,6-Et2C6H3; L = PPh3 PMePh2) have been prepared from [IrCl(CO)L2] and the corresponding aryllithiums. With the exception of trans-[Ir(2-EtC6H4)(CO)(PPh3)2] these compounds show cis, trans isomerism. After separation, the isomers have been studied by NMR (1H, 31P), IR, and UV-VIS spectroscopy. ab]Durch Umsetzung von [IrCl(CO)L2] (L = PPh3, PMePh2) mit den entsprechenden Lithiumarylen wurden ortho-substituierte Aryliridium(I)-Komplexe des Typs [Ir(Rn C6H5-n)(CO)L2] (RnC6H5?n = 2-EtC6H4; 2,6-Et2C6H3; 2-Et-6-MeC6H3) dargestellt. Mit Ausnahme von trans-[Ir(2-EtC6H4)(CO)(PPh3)2] zeigen diese Verbindungen die Erscheinung der cis,trans-Isomerie. Die Isomere wurden getrennt und mit Hilfe NMR- (1H, 31P), IR- und UV/VIS-spektroskopischer Methoden untersucht. 相似文献
Substituted phosphines of the type Ph2PCH(R)PPh2 and their PtII complexes [PtX2{Ph2PCH(R)PPh2}] (R = Me, Ph or SiMe3; X = halide) were prepared. Treatment of [PtCl2(NCBut)2] with Ph2PCH(SiMe3)-PPh2 gave [PtCl2(Ph2PCH2PPh2)], while treatment with Ph2PCH(Ph)PPh2 gave [Pt{Ph2PCH(Ph)PPh2}2]Cl2. Reaction of p-MeC6H4C≡CLi or PhC≡CLi with [PtX2{Ph2PCH(Me)PPh2}] gave [Pt(C≡CC6H4Me-p)2-{Ph2PCH(Me)PPh2}] (X = I) and [Pt{Ph2PC(Me)PPh2}2](X = Cl),while reaction of p-MeC6H4C≡CLi with [Pt{Ph2PCH(Ph)PPh2}2]Cl2 gave [Pt{Ph2PC(Ph)PPh2}2]. The platinum complexes [PtMe2(dpmMe)] or [Pt(CH2)4(dpmMe)] fail to undergo ring-opening on treatment with one equivalent of dpmMe [dpmMe = Ph2PCH(Me)PPh2]. Treatment of [Ir(CO)Cl(PPh3)2] with two equivalents of dpmMe gave [Ir(CO)(dpmMe)2]Cl. The PF6 salt was also prepared. Treatment of [Ir(CO)(dpmMe)2]Cl with [Cu(C≡CPh)2], [AgCl(PPh3)] or [AuCl(PPh3)] failed to give heterobimetallic complexes. Attempts to prepare the dinuclear rhodium complex [Rh2(CO)3(μ-Cl)(dpmMe)2]BPh4 using a procedure similar to that employed for an analogous dpm (dpm = Ph2PCH2PPh2) complex were unsuccessful. Instead, the mononuclear complex [Rh(CO)(dpmMe)2]BPh4 was obtained. The corresponding chloride and PF6 salts were also prepared. Attempts to prepare [Rh(CO)(dpmMe)2]Cl in CHCl3 gave [RhHCl(dpmMe)2]Cl. Recrystallization of [Rh(CO)(dpmMe)2]BPh4 from CHCl3/EtOH gave [RhO2(dpmMe)2]BPh4. Treatment of [Rh(CO)2Cl2]2 with one equivalent of dpmMe per Rh atom gave two compounds, [Rh(CO)(dpmMe)2]Cl and a dinuclear complex that undergoes exchange at room temperature between two formulae: [Rh2(CO)2(μ-Cl)(μ-CO)(dpmMe)2]Cl and [Rh2(CO)2-(μ-Cl)(dpmMe)2]Cl.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
The hydrides [MH(O2CCF3)(CO)(PPh3)2] (M = Ru or Os) react with disubstituted acetylenes PhCCPh and PhCCMe 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-PhHCCHMe 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(CCPh)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(CCPh)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(CHCH2)(O2CCF3)(CO)(PPh3)2]. 相似文献
The iridium(I) complex [Ir(CO2Me)(CO)2(PPh3)2] undergoes a transesterification reaction with the alcohols CH2C(R)CH2OH (R = H, Me), MeCCCH2CH2OH, and HOCH2CH2OH to afford the complexes [Ir(CO2CH2CH2CMe)(CO)2(PPh3)2] and [Ir(CO2CH2CH2OH)(CO)2(PPh3)2], respectively. In contrast the acetylenic alcohol HCCCH2CH2OH gives [Ir(CCCH2CH2OH)(CO)PPh3)2]. Some reactions of the new complexes are described. 相似文献
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
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
[OS(η2-CS2Me)(CO)2(PPH3)2]+ and [Ir(η2-CS2Me)Cl(CO)(PPh3)2)+ react with NaBH4 giving OsH(CS2Me)(CO)2(PPh3)2 and IrH(CS2Me)Cl(CO)(PPh3)2 respectively; These compounds contain mutually hydride and η1-dithiomethylester ligands and upon heating undergo 1,2-elimination of MeSH producing Os(CS)(CO)2(PPh3)2 and IrCl(CS)(PPh3)2. 相似文献
Reaction of Ru(CO)Cl(CHCHR)(PPh3)2 or Ru(CO)Cl(CHCHR)(PPh3)2L (L = py, Me2Hpz) with 1 equivalent of t-butyl isocyanide gives the alkenyl derivatives Ru(CO)Cl(CHCHR)(PPh3)2(t-BuNC). When an excess of isocyanide is used, further reaction results in intramolecular CO insertion to yield η1-acyl complexes [Ru(COCHCHR) (t-BuNC)3(PPh3)2]Cl. Related complexes were obtained from [Ru(CO)(CHCHR)(MeCN)2(PPh3)2]PF6 and an excess of isocyanide. 相似文献
Reaction of Cy3PCS2 (Cy = cyclohexyl) with the hydrido complexes [RuClH(CA)(PPh3)3] (A O, S), [RuH(CO)(NCMe)2(PPh3)2]+, and [RuH(OClO3)(CO)(CNtBu)(PPh3)2] leads to the complex cations [RuH(CA)(PPh3)2(η2-S2CPCy3)]+, [Ru(η2-S2CHPCy3)(CO) (PPh3)2]+, [RuH(η1-S2CPCy3)(CO)(CNtBu)(PPh3)2]+. The σ-vinyl complex [Ru(CHCHC6H4Me-4)Cl(CO)(PPh3)2] reacts with Cy3PCS2 to give the cationic complex [Ru(CHCHC6H4Me-4) (CO)(PPh3)2(η2-S2CPCy3)]+, but this complex is not formed by hydroruthenation of HCCC6H4Me-4 by [RuH(CO)(PPh3)2(η2-S2CPCy3)]+. The inter-relationships between the above complexes are discussed. 相似文献
6-Aminocoumarin reacts with pyridine-2-carboxaldehyde and has synthesized N-[(2-pyridyl)methyliden]-6-coumarin (L). The ligand, L, reacts with [Cu(MeCN)4]ClO4/AgNO3 to synthesize Cu(I) and Ag(I) complexes of formulae, [Cu(L)2]ClO4 and [Ag(L)2]NO3, respectively. While similar reaction in the presence of PPh3 has isolated [Cu(L)(PPh3)2]ClO4 and [Ag(L)(PPh3)2]NO3. All these compounds are characterized by FTIR, UV-Vis and 1H NMR spectroscopic data. In case of [Cu(L)(PPh3)2]ClO4 and [Ag(L)(PPh3)2]NO3, the structures have been confirmed by X-ray crystallography. The structure of the complexes are distorted tetrahedral in which L coordinates in a N,N′ bidentate fashion and other two coordination sites are occupied by PPh3. The ligand and the complexes are fluorescent and the fluorescence quantum yields of [Cu(L)(PPh3)2]ClO4 and [Ag(L)(PPh3)2]NO3 are higher than [Cu(L)2]ClO4 and [Ag(L)2]NO3. Cu(I) complexes show Cu(II)/Cu(I) quasireversible redox couple while Ag(I) complexes exhibit deposition of Ag(0) on the electrode surface during cyclic voltammetric experiments. gaussian 03 computations of representative complexes have been used to determine the composition and energy of molecular levels. An attempt has been made to explain solution spectra and redox properties of the complexes. 相似文献
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-CH2CRCHCH2)(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
Si?F bond cleavage of fluoro‐silanes was achieved by transition‐metal complexes under mild and neutral conditions. The Iridium‐hydride complex [Ir(H)(CO)(PPh3)3] was found to readily break the Si?F bond of the diphosphine‐ difluorosilane {(o‐Ph2P)C6H4}2Si(F)2 to afford a silyl complex [{[o‐(iPh2P)C6H4]2(F)Si}Ir(CO)(PPh3)] and HF. Density functional theory calculations disclose a reaction mechanism in which a hypervalent silicon species with a dative Ir→Si interaction plays a crucial role. The Ir→Si interaction changes the character of the H on the Ir from hydridic to protic, and makes the F on Si more anionic, leading to the formation of Hδ+???Fδ? interaction. Then the Si?F and Ir?H bonds are readily broken to afford the silyl complex and HF through σ‐bond metathesis. Furthermore, the analogous rhodium complex [Rh(H)(CO)(PPh3)3] was found to promote the cleavage of the Si?F bond of the triphosphine‐monofluorosilane {(o‐Ph2P)C6H4}3Si(F) even at ambient temperature. 相似文献
The reactions of the complexes CpCo(CO)L (Cp = cyclopentadienyl, L = CO, PPh3) with ClCH2CN have been investigated. Chloroacetonitrile reacts with CpCo(CO)PPh3 to give the cationic complex [CpCo(CH2CN)(CNCH2Cl)PPh3]+, which has been isolated and characterized. Compounds of the type [CpCo(CH2CN)(bipy)]+ BPh4? and CpCo(CH2CN)PPh3CN have been obtained by substitution reactions. 相似文献
Treatment of RuHCl(CO)(L)3 with a slight excess amount of K[HB(3,5-Me2pz)3] in boiling MeOH solution yielded unusual 3,5-dimethylpyrzaole (Hdmpz) complexes, RuHCl(CO)(Hdmpz)(L)2 (L=PPh3, 1 or AsPh3, 2). Unexpectedly the dissociation of the bonds between the boron atom and the nitrogen atoms of the potentially tridentate [HB(3,5-Me2pz)3]− ligand during the coordination of the ligand to the RuII metal has been observed. In a separate preparation, the RuHCl(CO)(Hdmpz)(PPh3)2 complex has also been synthesized from the reaction between RuHCl(CO)(PPh3)3 and the monodentate Hdmpz ligand. Complexes 1 and 2 have been characterized by elemental analysis, IR and 1H NMR spectroscopies. Compound 1 has also been prepared by the reaction between RuHCl(CO)(PPh3)3 and K[H2B(3,5-Me2pz)2] in boiling toluene solution. The crystal structure of 2 has been studied by X-ray crystallography. The geometrical structure around RuII of 2 is a distorted octahedral structure. The crystal structure of 2 consists of a discrete monomeric compound. It is interesting to find that the sterically-demanding [HB(3,5-Me2pz)3]− or [H2B(3,5-Me2pz)2]− ligands break up during the reaction with the RuII complexes to form the neutral 3,5-dimethylpyrazole complexes. In contrast to these observations, [H2Bpz2]− and [H2B(4-Brpz)2]− ligands form very stable RuII complexes. 相似文献
