The substitution reaction trans-[Ru(NH3)4P(III)pz]2+ + H2O where P(III) = PEt3, PBu3, PPh3, P(OBu)3 and P(OPh)3 has been studied at 25.0°C, μ = 0.10 NaCF3COO, CH+ = 1.0×10−3 M. Assuming the second order specific rate k1 for the substitution of the water molecule on the coordination sphere for pz as indicative of a relative order of the trans-effect of P(III), the following increasing trans-effect order can be written: P(OPh)3<PPh3<P(OEt)3< P(OBu)3<PBu3<PEt3. The weakening of the Ru(II)pz bond expressed as 1/Keq permits us to write the following order of increasing trans-influence: PEt3<PBu3<P(OBu)3<P(OEt)3∼ PPh3<P(OPh)3. The complex trans-[Ru(NH3)4- (PEt3)(P(OEt)3)](PF6)2 has been isolated and characterized by microanalysis, electronic and voltammetric spectra. The aquation of this complex provides additional support to the generalizations about the influence of π bonding on the trans-influence of phosphanes. 相似文献
The readily available dialkyl H-phosphonates (RO)2P(O)H, where R = Me, Et, iPr, nBu and Bn can be mono-dealkylated by heating at reflux in excess tert-butylamine. Where R = Me or Bn then crystals of [(CH3)3CNH3]+ [ROP(O)HO]− form in the reaction vessel on overnight standing. 相似文献
Reaction of cis-[Ru(acac)2(η2-C8H14)2] (1) (acac = acetylacetonato) with two equivalents of PiPr3 in THF at −25 °C gives trans-[Ru(acac)2(PiPr3)2], trans-3, which rapidly isomerizes to cis-3 at room temperature. The poorly soluble complex [Ru(acac)2(PCy3)2] (4), which is isolated similarly from cis-[Ru(acac)2(η2-C2H4)2] (2) and PCy3, appears to exist in the cis-configuration in solution according to NMR data, although an X-ray diffraction study of a single crystal shows the presence of trans-4. In benzene or toluene 2 reacts with PiPr3 or PCy3 to give exclusively cis-[Ru(acac)2(η2-C2H4)(L)] [L = PiPr3 (5), PCy3 (6)], whereas in THF species believed to be either square pyramidal [Ru(acac)2L], with apical L, or the corresponding THF adducts, can be detected by 31P NMR spectroscopy. Complexes 3-6 react with CO (1 bar) giving trans-[Ru(acac)2(CO)(L)] [L = PiPr3 (trans-8), PCy3 (trans-9)], which are converted irreversibly into the cis-isomers in refluxing benzene. Complex 5 scavenges traces of dinitrogen from industrial grade dihydrogen giving a bridging dinitrogen complex, cis-[{Ru(acac)2(PiPr3)} 2(μ-N2)] (10). The structures of cis-3, trans-4, 5, 6 and 10 · C6H14 have been determined by single-crystal X-ray diffraction. Complexes trans- and cis-3, 5, 6, cis-8, and trans- and cis-9 each show fully reversible one-electron oxidation by cyclic voltammetry in CH2Cl2 at −50 °C with E1/2(Ru3+/2+) values spanning −0.14 to +0.92 V (versus Ag/AgCl), whereas for the vinylidene complexes [Ru(acac)2 (CCHR)(PiPr3)] [R = SiMe3 (11), Ph (12)] the process is irreversible at potentials of +0.75 and +0.62 V, respectively. The trend in potentials reflects the order of expected π-acceptor ability of the ligands: PiPr3, PCy3 <C 2H4 < CCHR < CO. The UV-Vis spectrum of the thermally unstable, electrogenerated RuIII-ethene cation 6+ has been observed at −50 °C. Cyclic voltammetry of the μ-dinitrogen complex 10 shows two, fully reversible processes in CH2Cl2 at −50 °C at +0.30 and +0.90 V (versus Ag/AgCl) corresponding to the formation of 10+ (RuII,III) and 102+ (RuIII,III). The former, generated electrochemically at −50 °C, shows a band in the near IR at ca. 8900 cm−1 (w1/2 ca. 3700 cm−1) consistent with the presence of a valence delocalized system. The comproportionation constant for the equilibrium 10 + 102+ ? 2 10+ at 223 K is estimated as 1013.6. 相似文献
Four ruthenium (II) complexes of general formula Ru(PPh3)2(L)2 have been synthesized and characterized. The spectroscopic and cyclic voltammetric studies of these complexes are also reported. X-ray crystal structure determination of two of the complexes reveal that Ru(II) occupies trans,trans,trans-(t,t,t) N2O2P2 centrosymmetric octahedral environments, with the ligand pair occupying the equatorial plane. 31P NMR confirms the presence of two trans-PPh3 groups in all the complexes. The transformation of the complexes in dichloromethane solution is studied by spectrophotometry and 31P NMR spectroscopy. 相似文献
The hydroxo complex [NBu4]2[Ni2(C6F5)4(μ-OH)2] reacts with ammonium O,O′-dialkyldithiophosphates, O-alkyl-p-methoxyphenyldithiophosphonate acids and ammonium O-alkylferrocenyldithiophosphonates in dichloromethane under mild conditions to give, respectively, [NBu4][Ni(C6F5)2{S(S)P(OR)2}] (R=Me (1), Et (2), iPr (3)) and [NBu4][Ni(C6F5)2{S(S)P(OR)Ar}] (Ar=p-MeOC6H4, R=Me (4), Et (5), iPr (6); Ar=ferrocenyl; R=Me (7), Et (8), iPr (9)). The monothiophosphonate nickel complexes [NBu4][Ni(C6F5)2{S(S)P(OR)(ferrocenyl)}] (R=Et (10), iPr (11)) are obtained by reaction of the hydroxo complex with O-alkylferrocenyldithiophosphonate acids. Analytical (C, H, N, S), conductivity, and spectroscopic (IR, 1H, 19F and 31P NMR, and FAB-MS) data were used for structural assignments. A single-crystal X-ray diffraction study of [NBu4][Ni(C6F5)2{S(S)P(OMe)(p-MeOC6H4)}] (4) and [NBu4][Ni(C6F5)2{S(O)P(OEt)(ferrocenyl)}] (10) shows that in both cases the coordination around the nickel atom es essentially square planar with NiC2S2 and NiC2SO central cores, respectively. 相似文献
Substitution reaction of chloro η6-arene ruthenium N∩O-base complexes [(η6-arene)Ru(N∩O)Cl] [N∩O = pyrazine-2-carboxylic acid (pca-H), 8-hydroxyquinoline (hq-H); arene = p-iPrC6H4Me, N∩O = hq (1); arene = C6Me6, N∩O = hq (2)] with NaN3 yield the neutral arene ruthenium azido complexes of the general formula [(η6-arene)Ru(N∩O)N3] [N∩O = pca, arene = p-iPrC6H4Me (3), arene = C6Me6 (4); N∩O = hq, arene = p-iPrC6H4Me (5), arene = C6Me6 (6)]. These complexes undergo [3 + 2] dipolar cycloaddition reaction with activated alkynes dimethyl and diethyl acetylenedicarboxylates to yield the arene triazole complexes [(η6-arene)Ru(N∩O){N3C2(CO2R)2}] [N∩O = pca, R = Me, arene = p-iPrC6H4Me (7), C6Me6 (8); R = Et, arene = p-iPrC6H4Me (9), C6Me6 (10); N∩O = hq, R = Me, arene = p-iPrC6H4Me (11) C6Me6 (12); R = Et, arene = p-iPrC6H4Me (13), C6Me6 (14)]. On the bases of proton NMR study, in the above triazole complexes N(2) isomers are assigned with dimethylacetylenedicarboxylate whereas N(1) isomers with diethylacetylenedicarboxylate. All complexes have been characterized by IR and NMR spectroscopy as well as by elemental analysis. The molecular structures of the azido complexes [(η6-p-iPrC6H4Me)Ru(pca)N3] (3), [(η6-p-iPrC6H4Me)Ru(hq)N3] (5) and [(η6-C6Me6)Ru(hq)N3] (6) have been established by single crystal X-ray diffraction studies. 相似文献
The reaction of cis- or trans-[Ru(CNtBu)4(CN)2] with Fe(III) compounds leads to the formation of molecular squares of the general formula cyc-[Ru(CN-tBu)4(CN)2FeX3]2 or one-dimensional coordination polymers [Ru(CN-tBu)4(CN)2FeX3]n, respectively. Temperature dependent susceptibility measurements indicate that the magnetic properties of the coordination compounds are determined by their molecular structure. Of particular importance is the local symmetry at the iron(III) center which is related to the coordinating anion. The magnetic properties are best described in terms of weak antiferromagnetic interactions between the iron centers for the molecular squares as well as the coordination polymer with X = NO3 and as weak ferromagnetic interactions in case of the linear coordination polymer with X = Cl. For all compounds zero field splitting at low temperatures has to be taken into account. 相似文献
The reaction of 2,3-tri with CrCl3·6H2O1, dehydrated in boiling DMF, results in the formation of mer-CrCl3(2,3-tri) and anation of hydrolysed solutions of mer-MCl3(2,3,-tri) (M=Co, Cr) with 6 M HCl containing HClO4, forms trans-dichloro- mer-[MCl2(2,3-tri)(OH2)]ClO4·H2O (M=Cr, Co; I, II). trans-Dinitro-mer-[Co(NO2)2(NH3)(2,3-tri)] ClO4 crystallises from the reaction between mer-Co(NO2)3(2,3-tri) and aqueous 7 M ammonia, on addition of NaClO4·H2O, and trans-dichloro-mer-[CoCl2(NH3)(2,3-tri)]ClO4 (III) can be isolated by treatment of the dinitro with 12 M HCl. Reaction of mer-CoCl3(2,3-tri) with C2O42−, followed by addition of aqueous NH3 and NaClO4·H2O results in the isolation of racemic mer-[Co(ox)(NH3)(2,3-tri)]ClO4· H2O. This complex was resolved into its enantiomeric forms and treatment of these with SOCl2/MeOH/ HClO4 gave the chiral forms of trans-dichloro-mer- [CoCl2(NH3)(2,3-tri)]ClO4 (R or S at the see-NH center). The rates of loss of the first chloro ligand from these dichloro complexes have been measured spectrophotometrically in 0.1 M HNO3 over a 15 K temperature range to give the following kinetic parameters; (I) kH(298)=7.25 × 10−5 s−1, Ea=78.5 kJ mol−1, δS298#=−69 J K−1 mol−1; (II) kH(298)=4.00 × 10−3 s−1, Ea=89.9, δS298#= +87.5; (III) kH(298)=3.09 × 10−4 s−1, Ea=103, δS298#=+27. Treatment of the dichloro cations with Hg2+/HNO3 results in the generation of mer- M(2,3-tri)(OH2)33+ (M=Cr, Co; IV, V) and trans- diaqua-mer-Co(NH3)(2,3-tri)(OH2)23+ (VI). The Co(III) cations isomerise to the fac configuration with (V) Kisom(298) μ=1.0 M)=2.97 × 10−5 s−1, Ea=115, δS298#=+46. (VI) Kisom(298) (μ=1.0 M)=4.13 × 10−5 s−1, Ea=113, δS298#=+52. 相似文献
Described are the syntheses and structures of a phosphonium salt of the anionic ligand O-t-butyl-1,1-dithiooxalate, [PPh3Bz][i-dtotBu] ([PPh3Bz][1]), and of two Cu(I) complexes of this anion, Cu(PPh3)2(η2-i-dtotBu) (2) and Cu(dmp)(PPh3)(η1-i-dtotBu) (3, dmp = 2,9-dimethyl-1,10-phenanthroline). In addition, it was found that the reaction of CuBr2 with i-dtotBu− gives a O-t-butyl-1-perthio-1-thiooxalato complex of copper(I), [BzPh3P][Cu(Br)(S-i-dtotBu)] ([BzPh3P][4]), where [S-i-dtotBu]− is a disulfide-containing anionic ligand. The electronic structure and absorption spectrum of this species were investigated by time dependent DFT methods. 相似文献
The reactions of aminobis(phosphines), Ph2PN(R)PPh2 (R = H, Me, Et, nPr, nBu, Ph), with Me2Pt(COD) led to the formation of four-membered metallacycles in good yield. The enthalpies of the ligand substitution reactions are measured by the anaerobic solution calorimetry in THF at 30 °C. 相似文献
The mononuclear cations of the general formula [(η6-arene)RuCl(pdpt)]+ (pdpt = 5,6-diphenyl-3-(pyridine-2-yl)-1,2,4-triazine; arene = C6H6 (1); C6H5Me (2); p-PriC6H4Me (3); C6Me6 (4)) have been synthesised from 5,6-diphenyl-3-(pyridine-2-yl)-1,2,4-triazine (pdpt) and the corresponding chloro complexes [(η6-C6H6)Ru(μ-Cl)Cl]2, [(η6-C6H5Me)Ru(μ-Cl)Cl]2, [(η6p-PriC6H4Me)Ru(μ-Cl)Cl]2 and [(η6-C6Me6)Ru(μ-Cl)Cl]2, respectively. The X-ray crystal structure analyses of [1][PF6] · (C6H6)2.5 and [2][PF6] · (CH3CN)2 reveal a typical piano-stool geometry around the metal centre and in the crystal packing a complexed networks of intermolecular interactions. 相似文献
cis,cis,trans-[PtIV(NH3)2Cl2(OH)2] reacts reversibly with ascorbic acid to give dehydroascorbic acid and mainly cis-[PtII(NH2Pri)2Cl2]. The parameters for the forward reaction are: kf = 0.584 M− s− at 37.0 °C, ΔH≠f = 108.6 −+ 6.4 kJ mol−1 andΔS≠f = 101 −+ 22 J K−1 mol−1. 相似文献
The reaction of the dihydrido iridium(III) precursor [IrH2(Cl)(PiPr3)2] (5) with internal alkynes RCC(CO2Me) (R = Me, CO2Me) afforded the five-coordinate hydrido(vinyl) complexes [IrH(Cl){(E)-C(R)CH(CO2Me)}(PiPr3)2] (6, 7), via insertion of the alkyne into one of the IrH bonds. Compounds 6 and 7 are also accessible by careful hydrogenation of the alkyne iridium(I) derivatives trans-[IrCl{RCC(CO2Me)}(PiPr3)2] (9, 10), the latter being prepared from in situ generated trans-[IrCl(C8H14)(PiPr3)2] and RCC(CO2Me). UV irradiation of 6 (R = CO2Me) led to the formation of the isomer [IrH(Cl){κ2(C,O)-C(CO2Me)CHC(OMe)O}(PiPr3)2] (3) having the vinyl ligand coordinated in a bidentate fashion. While 6 reacted with acetonitrile and CO to afford the six-coordinate iridium(III) compounds [IrH(Cl){(E)-C(CO2Me)CH(CO2Me)}(L′)(PiPr3)2] (11, 12), treatment of 6 with LiC5H5 gave the half-sandwich-type complex [(η5-C5H5)IrH{(E)-C(CO2Me)CH(CO2Me)}(PiPr3)] (13) by, the loss of one PiPr3. The reaction of 3 with CO under pressure resulted in the formation of [IrH(Cl){(Z)-C(CO2Me)CH(CO2Me)}(CO)(PiPr3)2] (14) in which, in contrast to the stereoisomer 12, the two CO2Me substituents are trans disposed. 相似文献
Reaction of the lithium salts of N,N′-dialkyl-2-amino-4-imino-pent-2-enes, nacnacRLi(THF) (R = CH2Ph, Cy, nPr, iBu or S-CH(Me)Ph), with half an equivalent of CrCl2(THF)x yielded the homoleptic complexes (nacnacR)2Cr. All complexes were characterized by X-ray diffraction studies and displayed a highly symmetric, square-planar coordination around the chromium center with strong boat-like distortions of the diketiminate ligands. Reaction of nacnacRLi(THF) (R = CH2Ph, Cy) with one equivalent of CrCl2(THF)x afforded the dimeric complexes {nacnacRCr(μ-Cl)}2. 相似文献
Energy-transfer rate-constants from photo-excited [Ru(N–N)3]2+ (N–N = 2,2′-bipyridine (bpy), 4,4′-dimethyl-2,2′-bipyridine (4dmb), 5,5′-dimethyl-2,2′-bipyridine (5dmb)) to [Cr(O–O)3]3− (O–O2− = ox2− ((COO−)2), mal2− (CH2(COO−)2)) and [Cr(CN)6]3− in encounter complexes were evaluated in aqueous solutions containing alkali metal ion. The rate constant depends on the molecular size of the ruthenium(II) complex: 1.8 × 108 s−1 for [Ru(bpy)3]2+ (molecular radius, r = 5.8 Å), 1.4 × 108 s−1 for [Ru(5dmb)3]2+ (r = 6.1 Å) and 0.96 × 108 s−1 for [Ru(4dmb)3]2+ (r = 6.7 Å) in the system of [Ru(N–N)3]2+–[Cr(ox)3]3− in aqueous solution. However, the rate constant is much more sensitive to the chromate(III) complex than to ruthenium(II) complex; 1.8 × 108 s−1 and 0.43 × 108 s−1 for [Cr(ox)3]3− (r = 4.0 Å) and [Cr(mal)3]3− (r = 4.2 Å) in the [Ru(bpy)3]2+–[Cr(O–O)3]3− systems, respectively. We conclude that the congeniality between the donor’s and acceptor’s ligands in encounter complex plays an important role in energy transfer in aqueous solution. 相似文献
The reaction of the ruthenium complexes RuCl2(PPh3)3, RuCl2(PPh3)4, RuCl2(PMe3)4, RuCl2(Me2SO)4, or RuBr2(PPh3)3 with the tripod tetrakis(tertiary) phosphine P(CH2CH2CH2PMe2)3 gave the compounds cis-RuCl2 [P(CH2CH2CH2PMe2)3] (1) and cis-RuBr2[P(CH2CH2CH2PMe2)3] (2). The coordination geometry of 1 and 2 was derived from the ABX2 type 31P NMR patterns of the complexes, as well as from an X-ray structure determination for the chloride 1. Crystals of 1 were found to be monoclinic, space group P21/n (Z = 4), with a = 942.0(3), b = 1446.2(4), c = 1680(1) pm, and β = 104.99(4)°. Anisotropic refinement of the structure converged at R = 0.040 and Rw = 0.034 (3318 data). Selected bond lengths are (in pm): RuP(CH2−)Me2 (trans-atom P), 235.8(1) and 239.3(1); RuP(CH2−)Me2 (trans-atom Cl), 227.9(1); RuP(CH2−)3, 225.3(1); RuCl (trans-group P(CH2−)3), 252.1(1); and RuCl (trans-group P(CH2)Me2), 250.5(1). Reaction of 1 with LiAlH4 yielded the hydro derivatives cis-Ru(H)Cl[P(CH2CH2CH2PMe2)3] (3) and cis-RuH2[P(CH2CH2CH2PMe2)3] (4), which were characterized by IR and 1H and 31p NMR spectroscopy. 相似文献
A novel ruthenium(II) complex of dipyridophenazine (DPPZ) with the ancillary ligand imidazole[4,5-f] [1,10]phenanthroline (IP), [Ru(IP)2(DPPZ)] (PF6)2, has been synthesized and characterized by elemental analysis, 1D and 2D 1H NMR, fast-atom bombardment mass spectra (FABMS), electronic spectroscopy and cyclic voltammetry. The DNA-binding properties of the complex were studied by spectroscopic methods. The intrinsic binding constant, K =2.1 × 107M−1, of the complex to calf thymus DNA has been determined by absorption titration in 5 mmol dm−3 Tris-HCl, 50 mmol dm−3 NaCl buffer (pH 7.0). The excited state lifetimes and luminescence quenching with [Fe(CN)6]4− as the quencher in the presence of DNA were also tested and mono-exponentiality was observed for the emission decay curves. Viscosity measurements together with the optical titrations unambiguously proved that the complex bound with DNA intercalatively and that the binding affinity to DNA was several times larger than that of the parent complex [Ru(bpy)2(DPPZ)]2+. 相似文献
Both the trans and cis isomers of [Ru(acac)2{P(OMe)3}2] were isolated in the form of single crystals and characterized by single crystal X-ray diffraction, UV-Vis, MS, 1H, 13C and 31P NMR spectroscopy. The compounds of ruthenium(II), both mononuclear complexes, crystallize in triclinic space group. The metal ion in both compounds has similar, slightly distorted octahedral coordination geometry. Both complexes were tested as catalyst in hydrogen generation from the hydrolysis of sodium borohydride. When used alone, none of the trans- and cis-[Ru(acac)2{P(OMe)3}2] complexes shows significant catalytic activity. However, the catalytic activity of cis-[Ru(acac)2{P(OMe)3}2] in the hydrolysis of sodium borohydride is significantly enhanced by the addition of two equivalents of trimethylphosphite per ruthenium into the medium. 相似文献
A kinetic study of the oxidation of (hydroxyethyl)ferrocene (HEF) by [2-pyridylmethylbis(2-ethyl-thioethyl)ainine]copper(II) (Cu(pmas)2+) is reported, with the objective of documenting the influence of the two thioether sulfur ligands on the electron transfer rate. Both reactants exhibit a first-order dependence at pH 6, I = 0.1 M(NaNO3); k(25°C) = 1.3 × 104M−1sec−1, ΔH3 = 10.1 kcal/mole, ΔS3 = −6 eu. The apparent Cu(pmas)2+/+ self-exchange electron transfer rate constant calculated from this reaction on the basis of relative Marcus theory (4.7 × 101M−1 sec−1) agrees well with previous findings on ferrocytochrome c, Fe(CN)64−, and Ru(NH3)5py2+ oxidations. Spectrophotometric titrations of Cu(pmas)2+ and Cu(tmpa)2+ (tmpa = tris(2-pyridylmethyl)amine) with azide ion showed that both Cu(pmas)N3)+ (Kf1 = 3.1 × 103M−1) and Cu(pmas)(N3)2 (Kf2 = 3.5 × 101M−1) but Cu(tmpa)(N3)+ (Kf = 6.6 × 102M−1) are formed up to 0.15 M N3− (25°C, pH 6, I = 0.2 M), suggesting that a thioether sulfur atom is displaced in the uptake of a second N3− ion by Cu(pmas)(N3)+. The effect of thioether sulfur displacement by azide ion on the HEF-Cu(pmas)2+ reaction rate may be understood entirely through the tendency of N3− to shift the position of the redox equilibrium towards the reactant side, without invoking any special role for the sulfur ligand in promoting electron transfer reactivity. 相似文献
Reaction of iPrHPCH2PHiPr with [Ru3(CO)12] in the presence of [(Ph3P)2N]CN catalyst gave sequentially [Ru3(CO)10(μ-iPrHPCH2PHiPr)] and [Ru3- (CO)9(μ-H)(μ3-iPrHPCH2PiPr)]. The former complex exists in two isomeric forms. The structures were determined by 1H and 31P NMR spectroscopy. 相似文献
