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1.
《Inorganica chimica acta》1986,115(2):187-192
195-Platinum NMR spectra are reported for a series of complexes of bidentate ligands [Pt(LL)X4] (X=Cl, Br; LL=diphosphine, diarsine, dithioether, diselenoether), [Pt(Me2PCH2CH2PMe2)2X2]X2, [Pt(o-C6H4(AsMe2)2)2X2]X2, and for the Pt(II) analogues. The trends in chemical shifts δ(Pt) and 1J(PtP), 1J(PtSe) coupling constants are discussed, and used to establish the nature of the solution species obtained by oxidation of Pt(II) complexes of some multidentate phosphorus and arsenic ligands. The [Pt(LL)I4] materials are shown to exist as [PtII(LL)I2] in dimethylsulphoxide solution, but [Pt(o-C6H4(AsMe2)2)2I2]2+ is a genuine Pt(IV) iodo-complex.  相似文献   

2.
Rate parameters have been obtained for the oxidation of cuprous stellacyanin by cobalt(III) ions of the form cis(N)-[CoN2O4]?, including cis(N)-[Co(NTA)(gly)]?, cis(N)-[Co(IDA)2]?, [Co(en)(ox)2]?(μ 0.5 M(phosphate), pH 7.0), and Co(EDTA)?(μ 0.1 M(NaCl), pH 7.2, 0.001 M phosphate). An excellent isokinetic correlation between the activation parameters ΔH and ΔS exists for the reactions of aminopolycarboxylatocobalt(III) ions with reduced stellacyanin (β = 300 ± 12 K; correlation coefficient = 0.995). It is concluded that enthalpy-entropy compensation in these reactions may be understood in terms of differing orientations preferred by the various oxidants in forming precursor complexes with the reduced blue protein. While ΔH and ΔS values for electron transfer from stellacyanin to cis(N)-[CoN2O4]? ions vary over ranges of 10.7 kcal/mol and 34 cal/mol-deg, respectively, room temperature rate constants are relatively constant (3.6–34.5 M?1 sec?1), as expected from Marcus theory for outer sphere electron transfer.  相似文献   

3.
Six new dinuclear complexes, derived from cis-[Co(H2O)2(NH3)4]3+, cis-[Co(H2O)2(en)2]3+ and [M(CN)42? (M = Ni, Pd, Pt) were prepared and characterized by means of chemical analysis, electronic and IR measurements. The influence of the pH on the rate of the reaction was studied for the two derivatives of [Pd(CN)4]2?, showing that the best conditions to obtain the dinuclear compounds are at pH near 6, where the predominant species are cis-[Co(OH)(H2O)(amine)2]2+. The [Pt(CN)4]2? derivatives show PtPt interactions both in the solid state and in solution.  相似文献   

4.
The action of [Co(X)(NO)2]2 (X = Cl, Br, L) on [V(H)(CO)6?nLn] (L = 1/ndi- and tritertiary phosphine; n = 2, 3) in thf yields [V(CO)5?n(NO)L2] and [V(NO)2(thf)4]X as the two main products. Thf is easilty replaced by other ligands L′, leading to the complexes cis-[V(NO)2(thf)4?nL′n]X, where n = 1 to 4. In the case of L′= CNR (R = Cy, iPr, tBu), the species [VX(NO)2L′3] are formed. The presence of X in the first coordination sphere is established by the normal halogen dependence (Cl < Br < I) of 51V shielding.δ(51V) values have been obtained for the two series of complexes and compared with δ of other nitrosylvanadium species, including [VX(NO)L′4]X. for [V(NO)2L′4]br, 51V shielding increases in the sequence {O} < {S} < NR3 < NCMe < AsEt3 < SbEt3 < PEt2Ph < P(OMe)3 < CNR, reflecting a general increase of shielding as the polarizability of the ligand function increases and its electronegativity decreases. Superimposed effects arising from electronic influences (PEtPh2) < PMe3 < P(OMe)3 and steric conditions (chelate-4 ring < 7 ring < 6 ring < 5 ring) are also discussed. Steric factors are especially pronounced in the [V(CO)3(NO)Ph2P(CH2)mPPh3] series (m = 1–4). The thermo-labile parent compound, [V(CO)5NO], has been characterized by its δ(51V) = ?1489 ppm at 245 K.  相似文献   

5.
《Inorganica chimica acta》1989,165(2):241-243
The compound [WI(CO)(NCMe)(dppm)(η2-MeC2Me)][BF4] reacts with carbon monoxide and tbutylisonitrile in CH2Cl2 at room temperature to give the substituted products [WI(CO)2(dppm)(η2-MeC2Me)][BF4] (1) and [WI(CO)(CNtBu)(dppm)(η2-MeC2Me)][BF4] (2) in good yield. The new complexes were fully characterised by elemental analysis, infrared, 1H and 13C NMR spectroscopy. 13C NMR spectroscopy suggests that the but-2-yne ligand is donating four electrons to the tungsten in these complexes.  相似文献   

6.
Six-coordinate cobalt(III) complex trans-[Co{o-C6H4(PPh2)2}2X2]ClO4, fac-[Co{PhP(CH2CH2PPh2)2}X3],cis-[Co{P(CH2CH2PPh2)3}X2]ClO4 and cis-β-[Co{-CH2P(Ph)CH2CH2PPh2}2X2]PF6 (X = Cl, Br) have been prepared by halogen oxidation of the Co(II) analogues, and characterised by IR, electronic and 31P NMR spectroscopy. The failure to obtain complexes with X = I, and with some related ligands is discussed, and the rather low stability of the above complexes is rationalised in terms of steric crowding at the metal centre.  相似文献   

7.
《Inorganica chimica acta》1988,149(2):177-185
CpRuCl(PPh3)2 reacted with excess R-DAB in refluxing toluene to give CpRuCl(R-DAB(4e)) (1a: R = i-Pr; 1b: R = t-Bu; 1c: R = neo-Pent; 1d: R =p-Tol). 1H NMR and 13C NMR spectroscopic data indicated that in these complexes the R-DAB ligand is bonded in a chelating 4e coordination mode.Reaction of 1a and 1b with one equivalent of [Co(CO)4] afforded CpRuCo(CO)3(R-DAB(6e)) (2a: R = i-Pr; 2b: R = t-Bu). The structure of 2b was determined by a single crystal X-ray structure determination. Crystals of 2b are monoclinic, space group P21/n, with four molecules in a unit cell of dimensions: a = 16.812(4), b = 12.233(3), c = 9.938(3) Å and β = 105.47(3)°. The structure was solved via the heavy atom method and refined to R = 0.060 and Rw = 0.065 for the 3706 observed reflections. The molecule contains a RuCo bond of 2.660(3) Å and a cyclopentadienyl group that is η5-coordinated to ruthenium [RuC(cyclopentadienyl) = 2.208(3) Å (mean)]. Two carbonyls are terminally coordinated to cobalt (CoC(1) = 1.746(7) and CoC(2) = 1.715(6) Å) while the third is slightly asymmetrically bridging the RuCo bond (RuC(3) = 2.025(6) and CoC(3) = 1.912(6) Å). The RuC(3)O(3) and CoC(3)O(3) angles are 138.4(5)° and 136.5(5)°, respectively. The t-Bu-DAB ligand is in the bridging 6e coordination mode: σ-N coordinated to Ru (RuN(2) = 2.125(4) Å), μ2-N′ bridging the RuCo bond and η2-CN coordinated to Co (RuN(1) = 2.113(5), CoN(1) = 1.941(4) and CoC(4) = 2.084(5) Å). The η2-CN′ bonded imine group has a bond length of 1.394(7) Å indicating substantial π-backbonding from Co into the anti-bonding orbital of this CN bond.1H NMR spectroscopy indicated that 2a and 2b are fluxional on the NMR time scale. The fluxionality of 6e bonded R-DAB ligands is rarely observed and may be explained by the reversible interchange of the σ-N and η2-CN′ coordinated imine parts of the R-DAB ligand.  相似文献   

8.
The kinetics of electron transfer from L-ascorbic acid [H2A] to oxidants, dichlorotetraaquoruthenium(III) [RuCl2(H2O)4]+, iminodiacetatoruthenium(III) [Ru(III)IMDA]+ and ethylenediaminetetraacetatoruthenate(III) [Ru(III)EDTA] exhibit a first order dependence both on L-ascorbic acid and oxidants and inverse first order dependence on hydrogen ion concentration. Kinetic, spectroscopic and thermodynamic parameters are reported for the formation of intermediate Ru(III) (1:1) and Ru(III)chelateascorbate (1:1:1) complexes during the oxidation of L-ascorbic acid. The results are interpreted in terms of a mechanism involving a rate-determining inner sphere one electron transfer from L-ascorbic acid to the oxidants used in the present investigation, followed by a subsequent and kinetically rapid transfer of the second electron of ascorbic acid to another molecule of the oxidant. A detailed discussion of the kinetic data, temperature and ionic strength dependence of the oxidation reactions is presented.  相似文献   

9.
Three new nickel complexes have been synthesized with the ligands Hbss (4-mercapto-2-thia-1-butylbenzene) and Hbsms (2-(benzylsulfanyl)-2-methyl-1-propanethiol). [Ni(bss)2] is a mononuclear complex with an S4 coordination environment. [Ni3(bss)4](BF4)2 and [Ni3(bsms)4](BF4)2 are linear trinuclear complexes that can be synthesized either directly from the ligands Hbss and Hbsms in a reaction with Ni(BF4)2, or via the mononuclear complexes [Ni(bss)2] and [Ni(bsms)2] in a reaction with Ni(BF4)2. These reactions have been monitored with ligand field spectroscopy. Crystals suitable for X-ray diffraction were obtained for [Ni3(bss)4](BF4)2. The complex crystallizes in the space group P21/c. The nickel centers are in a square-planar environment; two peripheral nickel centers with an S2S2 (S=thiolato; S=thioether) coordination environment and the central nickel ion with an S4 coordination environment.The mononuclear nickel complexes [Ni(bss)2] and [Ni(bsms)2] were reacted with FeCl2, resulting in the hetero-tetranuclear nickel-iron complexes [Ni(bss)2FeCl2]2 and [Ni(bsms)2FeCl2]2. All complexes were characterized by analytical and spectroscopic methods.  相似文献   

10.
The coordination chemistry of the metalloligand [Pt2(μ-S)2(PPh3)4] towards cobalt(II) and cobalt(III) centres has been explored using an electrospray ionisation mass spectrometry (ESI MS)-directed methodology. Reaction of [Pt2(μ-S)2(PPh3)4] with CoCl2·6H2O in methanol gave a green-yellow suspension of the known adduct [Pt2(μ-S)2(PPh3)4CoCl2], and the CoBr2 adduct could be similarly prepared. When in situ-generated [Pt2(μ-S)2(PPh3)4CoCl2] is reacted with 8-hydroxyquinoline (HQ) and base, the initial product is the cobalt(II) adduct [Pt2(μ-S)2(PPh3)4CoQ]+, which is then converted in air to the cobalt(III) adduct [Pt2(μ-S)2(PPh3)4CoQ2]+, isolated as its hexafluorophosphate salt. The corresponding picolinate (Pic) derivative [Pt2(μ-S)2(PPh3)4Co(Pic)2]+ was similarly prepared, however reaction of [Pt2(μ-S)2(PPh3)4], CoCl2·6H2O and 8-(tosylamino)quinoline (HTQ) produced only the cobalt(II) adduct [Pt2(μ-S)2(PPh3)4CoTQ]+. Reactions of [Pt2(μ-S)2(PPh3)4], CoCl2·6H2O and dithiocarbamates gave cobalt(III) complexes [Pt2(μ-S)2(PPh3)4Co(S2CNR2)2]+ [R = Et or R2 = (CH2)4], and proceeded much more rapidly, consistent with the known ability of the dithiocarbamate ligand to stabilize cobalt in higher oxidation states. A study of the fragmentation of cobalt(III) adducts by positive-ion ESI mass spectrometry indicated that [Pt2(μ-S)2(PPh3)4CoQ2]+ fragments to form the radical cation [Pt2(μ-S)2(PPh3)4]+, which could also be generated by ESI MS analysis of [Pt2(μ-S)2(PPh3)4] in methanol-NaOH solution. In contrast, the corresponding indium(III) derivative [Pt2(μ-S)2(PPh3)4InQ2]+, and the cobalt(III) dithiocarbamate [Pt2(μ-S)2(PPh3)4Co(S2CN(CH2)4)2]+ are much more reluctant to fragment under analogous conditions, and the differences are discussed in terms of cobalt(III) redox chemistry.  相似文献   

11.
Cyclic voltammograms of cis-diammineplatinum α-pyrrolidone-blue and -tan, [Pt4(NH3)8(C4H6NO)4]n+ (n = 5 and 6, respectively) show for either complex only one redox peak at 0.53 V (average potential of the anodic and cathodic peak potentials). Coulometry and UVVis spectra of bulk- electrolyzed solution indicated that the redox peak corresponds to the reaction [Pt4(NH3)8(C4H6NO)4]8+ + 4e ⇄ 2[Pt2(NH3)4(C4H6NO)2]2+. When cyclic voltammetry is carried out in a solution of [Pt4(NH3)8(C4H6NO)4]6+ or a platinum electrode adsorbed with [Pt4(NH3)8(C4H6NO)4]6+ is used in the presence of oxidizing agent in the solution, O2 gas generates from the electrode surface with large catalytic cathodic current at potentials below ca. 0.8 V. The O2 gas was confirmed to generate from water by GC-MS analysis. This abnormal O2 generation phenomenon is explained with cyclic reactions of chemical surface oxide formation on the electrode by the oxidizing agent and electrochemical reduction of the surface oxide. Oxygen gas generates from the reaction of [Pt4(NH3)8(C4H6NO)4]8+ or [Pt4(NH3)8(C4H6NO)4]6+ with OH produced in the course of the electrochemical reduction of the electrode surface oxide. The ability of [Pt4(NH3)8(C4H6NO)4]8+ and [Pt4(NH3)8(C4H6NO)4]6+ to oxidize OH into O2 has been reported previously.  相似文献   

12.
Reaction of 1,2-dichloroethane with PhP(CH2CH2SH)2 and caesium carbonate affords 1,10-diphenyl-1,10-diphospha-4,7,13,16-tetrathiacyclooctadecane (18P2S4) in high yield (ca. 90%). 18P2S4 slowly decomposes in solution to afford insoluble PhP(S)(CH2CH2SCH2CH2SCH2CH2)2P(S)Ph which was characterised by single crystal X-ray diffraction. Reaction of 18P2S4 with [Ni(H2O)6](BF4)2 or Fe(BF4)2 affords [M(18P2S4)](BF4)2 (M = Ni or Fe). The structure of [Ni(18P2S4)]2+ is a tetragonally distorted octahedron in which there are two short Ni-S bonds [2.2152(6) Å] and two long Ni-S bonds [2.9268(6) Å]. For comparison the structure of [Ni(9PS2)2]2+ was determined and found to a have a similar, but less marked distortion, in which the difference between the long and short bonds is ca. 0.5 Å. In contrast the structure of [Fe(18P2S4)]2+ is octahedral with approximately equal Fe-S bonds. The electrospray mass spectra of the cations [M(9PS2)2]2+ and [M(18P2S4)]2+ (M = Ni or Fe) all display ethene loss from the ligands as has been previously observed with trithiacyclononane complexes. The results of P-C and C-S bond rupture were also observed in the reaction of ruthenium(III) triflate with 9PS2 which unexpectedly afforded crystals containing [Ru2(S)2(18P2S4)2], in which the two ruthenium centres are bridged by two sulfides and the two 18P2S4 ligands coordinated only through the phosphine centres. Also present in the crystals was one equivalent of tetrathiacycloundecane (12S4).  相似文献   

13.
《Inorganica chimica acta》2004,357(2):571-580
Treatment of the ligand N-(2-mercaptoethyl)-3,5-dimethylpyrazole with [Pd(CH3COO)2]3 and reaction of [PdCl(μ-med)]2 with pyridine (py) or triphenylphosphine (PPh3) in the presence of AgBF4 produced the following complexes: [Pd(CH3COO)(μ-med)]2, [Pd(μ-med)(py)]2(BF4)2 and [Pd(μ-med)(PPh3)]2(BF4)2. Similar reactions carried out with 2,2-bipyridine (bpy) or 1,3-bis(diphenylphosphino)propane (dppp) produced [Pd(μ-med)(bpy)]x(BF4)x (x=1 or 2) and [Pd(μ-med)(dppp)]x(BF4)x (x=1 or 2). Treatment of [Pd(μ-med)(bpy)]x(BF4)x with [PdCl2(CH3CN)2] produced [Pd3Cl2(μ-med)2(bpy)2](BF4)2. Treatment of [Pd(μ-med)(dppp)]x(BF4)x with [PdCl2(CH3CN)2] produced a mixture of [Pd(μ-Cl)(dppp)]2(BF4)2 and [Pd(μ-med)2(dppp)]2+. X-ray crystal structures of [Pd(μ-med)(PPh3)]2(BF4)2 · 2CH3CN and [Pd(μ-med)(bpy)]2(BF4)2 · 0.5CH3OH are presented.  相似文献   

14.
《Inorganica chimica acta》1986,112(2):153-157
New complexes of the type cis-[MX2(PP′)] (M= Ni, Pd and Pt; X=Cl, Br, I or NCS and PP′=(m- FC6H4)2PCH2CH2PPh2 or (p-FC6H4)2PCH2CH2PPh2) have been synthesized and characterized on the basis of 31P{1H}NMR1H NMR, IR and UV spectroscopy, elemental analysis and magnetic susceptibility measurements. All these complexes are found to be low spin, diamagnetic and square planar. 31P{1H} spectra of these complexes exhibit extraordinarily large downfield coordination chemical shifts, J(31P31P′) and J(195pt31P) couplings are discussed. Ring contribution (ΔR) values for palladium and platinum complexes are calculated from 31P NMR data.  相似文献   

15.
The synthesis and characterisation of a series of dinuclear and polynuclear coordination compounds with 4-allyl-1,2,4-triazole are described. Dinuclear compounds were obtained for Mn(II) and Fe(II) with composition [M2(Altrz)5(NCS)4], and for Co(II) and Ni(II) with composition [M2(Altrz)4(H2O)(NCS)4](H2O)2. The crystal structure of [Co2(Altrz)4(H2O)(NCS)4](H2O)2 was solved at room temperature. It crystallizes in the monoclinic space group P21/n. The lattice constants are a = 18.033(3) Å, b = 13.611(2) Å, c = 15.619(3) Å, β = 92.04(2)° Z = 4. One cobalt ion has an octahedrally arranged donor set of ligands consisting of three vicinal nitrogens of 1,2-bridging triazoles (CoN = 2.14–2.15 Å), one terminal triazole nitrogen (CoN = 2.12 Å) and two N-bonded NCS anions (CON = 2.08 Å). The other Co(II) ion has the same geometry, but the terminal triazole ligand is replaced by H2O (CoO = 2.15 Å). The crystal structure is stabilised by hydrogen bonding through H2O molecules, S-atoms of the NCS anions and the lone-pair electron of the monodentate triazole. The magnetic exchange in the Mn, Co and Ni compounds is antiferromagnetic with J-values of ?0.4 cm?1, ?10.9 cm?1 and ?8.7 cm?1 respectively. The Co compound was interpreted in terms of an Ising model. For [Zn2(Altrz)5(NCS)2]∞[Zn(NCS)4], [Cu2(Altrz)3(NCS)4]∞ and [Cd2(Altrz)3(NCS)4]∞ chain structures are proposed. In the Cu compound thiocyanates appear to be present, bridging via the nitrogen atom, as deduced from the IR spectrum.  相似文献   

16.
The synthesis of diethyl (pyridin-2-, -3-, -4-ylmethyl)phosphate (2-pmOpe, 3-pmOpe, 4-pmOpe) ligands and their palladium (II) complexes of general formula trans-[PdCl2L2] (L = 2-pmOpe, 3-pmOpe,4-pmOpe) has been described. Pyridine phosphate derivatives were synthesized via the condensation of phosphorochloridic acid diethyl ester with an appropriate pyridinylmethanol in the presence of triethylamine. The compounds have been identified and characterized by IR, far-IR, 1H NMR, 31P NMR, 31P CP-MAS NMR and elemental analyses. The crystal and molecular structures of palladium (II) complexes, i.e., [PdCl2(2-pmOpe)2] and [PdCl2(4-pmOpe)2] determined by the X-ray diffraction method, are presented. In both structures, Pd(II) ions are four-coordinated by two chlorine atoms and two pyridine nitrogen atoms. The geometry of complexes is square-planar and adopt a trans configuration, which is consistent with preparation method.  相似文献   

17.
Reaction of [Co(CO)3(NO)] with [2-NMe3-closo-2-CB10H10] in refluxing CH2Cl2 affords the mono- and di-cobalt complexes [1-NMe3-2-CO-2-NO-closo-2,1-CoCB10H10] (3) and [2,7-{Co(CO)(NO)}-7-(μ-H)-1-NMe3-2-CO-2-NO-closo-2,1-CoCB10H9] (4), respectively, of which 4 contains formally both Co(I) and Co(-I) centers. Compound 4 reacts with CO to give 3, or with donor ligands L in the presence of Me3NO to afford simple substituted species, [1-NMe3-2-L-2-NO-closo-2,1-CoCB10H10] (compounds 5; L = PEt3, PPh3, CNBut).  相似文献   

18.
In dimethyl formamide as solvent aquacobalamine reacts with the triorganyl phosphites 3–7 to give the corresponding (diorganylphosphito-P)cobalamines, their new β-axial ligands [P(O)(OR)2] (3a–7a) being formed by partial hydrolysis. In methanol, however, additional methanolysis normally leads to (dimethylphosphito-P)cobalamine with the axial ligand [P(O)-(OMe)2] (2a). Exceptions are P(OCH2CH2NMe2)3 (4) giving a complex with the only partially methanolized chiral ligand [P(O)(OCH2CH2NMe2)- (OMe)] (4b), too, and the bicyclic phosphite 5 which is also coordinated in the unchanged, nonhydrolyzed form. All complexes are characterized by elementary analysis, electrophoresis, UVVis and 1H, 31P NMR spectra. The chirality of the cobalamine moiety causes diatropism of the two organyl groups in the prochiral ligands [P(O)(OR)2] which is well seen in the NMR spectra of the complexes with the methyl and phenyl derivatives 2a and 6a, whereas the spectra with ligands 3a and (in part) 4a are not resolved well enough to distinguish the two forms. With the chiral ligand 4b two diastereomers are obtained in different yields; this asymmetric induction is indicated by the intensities of the respective signals in the NMR spectra.  相似文献   

19.
《Inorganica chimica acta》2001,312(1-2):139-150
The reactions of cis-1,1′-[η55-(C5H3CO2Me)2]Mo2(CO)6 (1), in the presence of 1 equiv. of Me3NO, and [(η5-C5H4CO2Me)Mo(CO)3]2 (2) with dppe produce CO labilization and formation of the dinuclear zwitterions trans-1,1′-[η55-(C5H3CO2Me)2]Mo2(CO)5(dppe) (3) and disproportionation species [(η5-C5H4CO2Me)Mo(CO)2(dppe)]+ [(η5-C5H4CO2Me)Mo(CO)3] (4), respectively. Using the same method, the reactions of trans-1,1′-[η55-(C5H3CO2Me)2]Mo2(CO)6I2 and (η5-C5H4CO2Me)Mo(CO)3I with PPh3 in the presence of 1 and 2 equiv. of Me3NO yield trans-1,1′-[η55-(C5H3CO2Me)2]Mo2(CO)4(PPh3)2I2 (5) and (η5-C5H4CO2Me)Mo(CO)2(PPh3)I (6). The reactions of the several anionic carbonyl species {trans-1,1′-[η55-(C5H3CO2Me)2]Mo2(CO)6}2−, [(η55-C10H8)W2(CO)6]2− and [(η5-C5H4CO2Me)Mo(CO)3] with S2Ph2 give rise to the thiolate–fulvalene complexes cis-1,1′-[η55-(C5H3CO2Me)2]Mo2(CO)4(μ-SPh)2 (7) and (η55-C10H8)W2(CO)6(SPh)2 (8) and the thiolate-bridged dimer [(η5-C5H4CO2Me)Mo(CO)(μ-SPh)]2 (9). Treatment of 6 with 1 equiv. of HCCCCH and with (η5-C5H5)Mo(CO)(dppe)(CCCCH), in the presence of CuI at room temperature, afford the cyclopentadiene complexes (η5-C5H4CO2Me)Mo(CO)2(PPh3)(CCCCH) (10) and (η5-C5H4CO2Me)(PPh3)(CO)2Mo(CCCC)Mo(CO)(dppe)(η5-C5H5) (11), respectively. The reaction of (η5-C5H5)Mo(CO)(dppe)(CCCCH) with Co2(CO)8 yields [Co2{μ-HC2CC[Mo(CO)(dppe)(η5-C5H5)]}(CO)6] (12). All the new compounds have been characterized by analytical and spectroscopic methods.  相似文献   

20.
New five mono- and dinuclear Ir hydrido complexes with polydentate nitrogen ligands, [Ir(H)2(PPh3)2(tptz)]PF6 (1), [Ir2(H)4(PPh3)4(tptz)](PF6)2 · 2H2O (2 · 2H2O), [Ir(H)2(PPh3)2(tppz)]BF4 (3), [Ir2(H)4(PPh3)4(tppz)](BF4)2 (4) and [Ir2(H)4(PPh3)4(bted)](BF4)2 · 6CHCl3 (5 · 6CHCl3), were systematically prepared by the reactions of the precursor Ir hydrido complex [Ir(H)2(PPh3)2(Me2CO)2]X (X=PF6 and BF4) with 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz), 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) and 1,4-bis(2,2:6,2″-terpyridine-4-yl)benzene (bted), and their structures and properties were characterized in the solid state and in solution. Each of the Ir hydrido complexes with polydentate nitrogen ligands crystallographically described a unique coordination mode. Their 1H NMR spectra demonstrated unusual 1H NMR chemical shifts of pyridyl rings that are likely induced by the ring current effect of neighboring ligands.  相似文献   

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