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1.
Cátia Ornelas José Mesquita M. Helena Garcia Nelson Lopes Kalle Nättinen 《Inorganica chimica acta》2005,358(8):2482-2488
The bimetallic cyano-bridged [(η5-C5H5)(PPh3)2Ru(μ-CN)Ru(PPh3)2(η5-C5H5)][PF6] (1) was prepared by reaction of [(η5-C5H5)(PPh3)2RuCl] with N,N′-bis(cyanomethyl)ethylenediamine. The single crystal structure determined by X-ray diffraction showed crystallization on the triclinic P1 space group with a perfect alignment of the cyanide bridges. This accentric crystallization was explored having in view the NLO properties at the macroscopic level, determined by the Kurtz Powder technique. Besides the very low efficiency values for the second harmonic generation, the value obtained for the bimetallic complex 1 showed to be higher than one of the parent complex [(η5-C5H5)(PPh3)2RuCN] (2). 相似文献
2.
The reactivity of the bridged chloro borylene complex [μ-BCl{(η5-C5H4Me)Mn(CO)2}2] (2a) towards various protic reagents was studied. Reaction of 2a with isopropanol yielded the alkoxy borylene complex [μ-BOiPr{(η5-C5H4Me)Mn(CO)2}2] (3d) in very high yield. A further series of protic reagents HX (X=HS−, BF4−, Co(CO)4−) gave, in the presence of pyridine, the new amino borylene complex [1-(μ-B)-4-H-(NC5H5){(C5H4Me)Mn(CO)2}2] (5a), which represents the product of an unprecedented 1,4-hydroboration of pyridine. Complex 5a was fully characterised in solution by multinuclear NMR studies, in the solid state by X-ray diffraction, and was also subject to DFT-studies. 相似文献
3.
Robert J. Baker 《Inorganica chimica acta》2006,359(15):4797-4801
The reaction of [(η7-C7H7)Zr(η5-C5H5)] with two Lewis bases, tetramethylimidazolin-2-ylidene and PMe3, is reported and their stability probed via spectroscopic and theoretical methods. The strongly σ-basic N-heterocyclic carbene forms a stable adduct which has been structurally characterised, whilst the PMe3 ligand coordinates weakly to the metal centre. Variable temperature 31P NMR spectroscopy has been used to determine the activation energy for this process (ΔG‡ = 40.5 ± 1.9 kJ mol−1). DFT calculations have been performed on both complexes and the structures discussed. In addition, the enthalpies for the formation of these compounds have been calculated [ΔH0(Zr-IMe) = −56.3 kJ mol−1; ΔH0(Zr-PMe3) = −2.3 kJ mol−1] and show that the N-heterocyclic carbene forms a thermodynamically much more stable adduct than that with PMe3. 相似文献
4.
Patrick M. Jeffries 《Inorganica chimica acta》2008,361(11):3165-3170
Treatment of the ruthenium(II) diene complexes [(η2,η2-nbd)RuCl2]n or [(η2,η2-cod)RuCl2]n with 4 equiv. of methyllithium in the presence of N,N,N′,N′-tetramethylethylenediamine (tmed) yields the methyl complexes [Li(tmed)]2[(η2,η2-nbd)RuMe4] (1) and [Li(tmed)]2[(η3,η2-C8H11)RuMe3] (2), respectively, where nbd = norbornadiene and cod = 1,5-cyclooctadiene. In the latter compound, the cyclooctadiene ligand has been deprotonated to afford a η3,η2-1,2,3:5,6-cyclooctadienyl group. Both complexes were studied by 1H and 13C{1H} NMR spectroscopy, and the crystal structure of 2 was determined. One lithium atom in 2 is four-coordinate and bridges between one ruthenium-bound methyl group and one of the wingtip allylic carbon atoms in the η3,η2-C8H11 ligand. The other lithium atom is five-coordinate, and forms contacts with the other two Ru-Me groups and with the other wingtip carbon atom of the allyl unit. 相似文献
5.
Kazuhiro Kawabata 《Inorganica chimica acta》2005,358(6):2082-2088
[Ir(η5-C5Me5)(C8H4S8)] (1) [ = 2-{(4,5-ethylenedithio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithionate(2−)] was reacted with iodine in dichloromethane to afford one-electron- and two-electron-oxidized species [IrI(η5-C5Me5)(C8H4S8)] (2), [IrI(η5-C5Me5)(C8H4S8)](I3) (3) and [IrI(η5-C5Me5)(C8H4S8)](I5) (4). The oxidized species exhibit electrical conductivities of (1.1-5.0) × 10−6 S cm−1 measured for compacted pellets at room temperature. The X-ray crystal structures of the two-electron-oxidized complexes 3 and 4 revealed the Ir-I bonds for both of them and the presence of for 3 and ions for 4 as the counter anions. They have many S-S and S-I non-bonding contacts to form two-dimensional molecular interaction sheets in the solid state. 相似文献
6.
Wen-Feng Liaw Chung-Hung HsiehShie-Ming Peng Gene-Hsiang Lee 《Inorganica chimica acta》2002,332(1):153-159
The SS bond-activation of diorganyl disulfide by the anionic metal carbonyl fragment [Mn(CO)5]− gives rise to an extensive chemistry. Oxidative decarbonylation addition of 2,2′-dithiobis(pyridine-N-oxide) to [Mn(CO)5]−, followed by chelation and metal-center oxidation, led to the formation of [MnII(SC5H4NO)3]− (1). The effective magnetic moment in solid state by SQUID magnetometer was 5.88 μB for complex 1, which is consistent with the MnII having a high-spin d5 electronic configuration in an octahedral ligand field. The average Mn(II)S, SC and NO bond lengths of 2.581(1), 1.692(4) and 1.326(4) Å, respectively, indicate that the negative charge of the bidentate 1-oxo-2-thiopyridinato [SC5H4NO]− ligand in complex 1 is mainly localized on the oxygen atom. The results are consistent with thiolate-donor [SC5H4NO]− stabilization of the lower oxidation state of manganese (Mn(I)), while the O,S-chelating [SC5H4NO]− ligand enhances the stability of manganese in the higher oxidation state (Mn(II)). Activation of SS bond as well as OH bond of 2,2′-dithiosalicylic acid by [Mn(CO)5]− yielded [(CO)3Mn(μ-SC6H4C(O)O)2Mn(CO)3]2− (4). Oxidative addition of bis(o-benzamidophenyl) disulfide to [Mn(CO)5]− resulted in the formation of cis-[Mn(CO)4(SR)2]− (R=C6H4NHCOPh) which was employed as a chelating metallo ligand to synthesize heterotrinuclear [(CO)3Mn(μ-SR)3Co(μ-SR)3Mn(CO)3]− (8) possessing a homoleptic hexathiolatocobalt(III) core. 相似文献
7.
Matthew A. Cranswick Olivia Oorhles-Steele Nicolai Burzlaff Dennis L. Lichtenberger 《Inorganica chimica acta》2008,361(4):1122-1133
The metal-sulfur bonding present in the transition metal-thiolate complexes CpFe(CO)2SCH3, CpFe(CO)2StBu, CpRe(NO)(PiPr3)SCH3, and CpRe(NO)(PPh3)SCH3 (Cp = η5-C5H5) is investigated via gas-phase valence photoelectron spectroscopy. For all four complexes a strong dπ-pπ interaction exists between a filled predominantly metal d orbital of the [CpML2]+ fragment and the purely sulfur 3pπ lone pair of the thiolate. This interaction results in the highest occupied molecular orbital having substantial M-S π∗ antibonding character. In the case of CpFe(CO)2SCH3, the first (lowest energy) ionization is from the Fe-S π∗ orbital, the next two ionizations are from predominantly metal d orbitals, and the fourth ionization is from the Fe-S π orbital. The pure sulfur pπ lone pair of the thiolate fragment is less stable than the filled metal d orbitals of the [CpFe(CO)2]+ fragment, resulting in a Fe-S π∗ combination that is higher in sulfur character than the Fe-S π combination. Interestingly, substitution of a tert-butyl group for the methyl group on the thiolate causes little shift in the first ionization, in contrast to the shift observed for related thiols. This is a consequence of the delocalization and electronic buffering provided by the Fe-S dπ-pπ interaction. For CpRe(NO)(PiPr3)SCH3 and CpRe(NO)(PPh3)SCH3, the strong acceptor ability of the nitrosyl ligand rotates the metal orbitals for optimum backbonding to the nitrosyl, and the thiolate rotates along with these orbitals to a different preferred orientation from that of the Fe complexes. The initial ionization is again the M-S π∗ combination with mostly sulfur character, but now has considerable mixing among several of the valence orbitals. Because of the high sulfur character in the HOMO, ligand substitution on the metal also has a small effect on the ionization energy in comparison to the shifts observed for similar substitutions in other molecules. These experiments show that, contrary to the traditional interpretation of oxidation of metal complexes, removal of an electron from these metal-thiolate complexes is not well represented by an increase in the formal oxidation state of the metal, nor by simple oxidation of the sulfur, but instead is a variable mix of metal and sulfur content in the highest occupied orbital. 相似文献
8.
Ilia A. Guzei M. Esther Sánchez-Castro Marisol Cervantes-Vásquez M. Angeles Paz-Sandoval 《Inorganica chimica acta》2006,359(2):701-706
The determination of the solid state structure of Cp*Ru(2,4-dimethyl-η5-pentadienyl) (1), where Cp* = pentamethylcyclopentadienyl, fills the gap in the series of previously established structures of closely related compounds. Compound 1 does not exhibit the ideal CS symmetry and its conformation is intermediate between the CS-synperiplanar eclipsed and CS-antiperiplanar arrangements of the ligands. Density functional theory studies indicate that the CS-synperiplanar eclipsed, CS-antiperiplanar, and intermediate conformations of 1 and Cp*Rh(2,4-dimethyl-η5-pentadienyl)+ (2) do not differ by more than a few tenths of 1 kcal/mol. The geometrical features of cation 2 are similar to those of 1, and in both complexes the pentadienyl ligands are not planar. The metal-carbon distances to the Cp* ligands in 1 and 2 are comparable, while the metal-carbon distances to the pentadienyl moiety are somewhat shorter in the Ru complex. A study of the conformational flexibility of the Cp* ligand in 5610 organometallic complexes showed that it usually shields the central metal by 36.2(10)%, provided the metal-centroid(Cp*) distances are normalized to 2.28 Å. The corresponding values in 1 and 2 are 37.2% and 37.4%, respectively. 相似文献
9.
Reactions of the electron-deficient triosmium cluster [Os3(CO)9(μ3-η2-C9H6N)(μ-H)] (1) with various alkynes are described. Cluster 1 readily reacts with the activated alkyne dimethyl acetylenedicarboxylate (dmad) upon mild heating (65-70 °C) to give the adduct [Os3(CO)9(μ-C9H6N)(μ3-MeO2CCCHCO2Me)] (2). In contrast, a similar reaction of 1 with diphenylacetylene affords previously reported compounds [Os3(CO)10(μ-η2-C9H6N)(μ-H)] (3), [Os3(CO)9(μ-C4Ph4)] (4) and [Os3(CO)8{μ3-C(C6H4)C3Ph3}(μ-H)] (5) while with 2-butyne gives only the known compound [Os3(CO)7(μ-C4Me4)(μ3-C2Me2)] (6). The new cluster 2 has been characterized by a combination of spectroscopic data and single crystal X-ray diffraction analysis. 相似文献
10.
Reaction between [(C5H5)Co{P(O)(OEt)2}3]2UCl2 and neopentyl lithium affords the novel complex, [{η4-C5H5(CH2C(CH3)3)}Co{P(O)(OEt)2}3]2U, in which the uranium metal center has been dehalogenated and the neopentyl nucleophiles have attacked the cyclopentadienyl groups on the Kläui ([(C5H5)Co{P(O)(OEt)2}3]−) ligands. The uranium atom in the title compound possesses octahedral geometry defined by the oxygen atoms from two sets of tripodal oxygen ligands, while the cyclopentadienyl ligands are bound η4 to the cobalt atoms. The formation of this complex suggests that the Kläui ligand may not be a suitable ligand framework for supporting organometallic complexes of oxophilic early actinides. 相似文献
11.
Richard C.S. Wong Mei Lee Ooi Chin Fei Chee Guan Huat Tan 《Inorganica chimica acta》2005,358(4):1269-1273
The reaction of [CpCr(CO)3]2 (Cp = η5-C5H5) (1) with an equivalent of Bz2S3 at ambient temperature gave [CpCr(CO)2]2S (3) [L.Y. Goh, T.W. Hambley, G.B. Robertson, Organometallics 6 (1987) 1051], novel complexes of [CpCr(CO)2(SBz)]2 (4) and together with [CpCr(SBz)]2S (5) as main products. Thermolytic studies showed that 4 underwent complete decarbonylation to give [CpCr(SBz)]2S (5). Final thermal decomposition of 3 and 5 eventually yielded Cp4Cr4S4 (6) (Goh et al., 1987) after prolonged reaction at 100 °C. However, the reaction of [CpCr(CO)2]2 (CrCr) (2) with Bz2S3 was much slower at ambient temperature which required 72 h to complete eventually yielding 3 and 5. All the products have been characterized by elemental and spectral analyses. 4 has been structurally determined. 相似文献
12.
A series of water soluble molybdenocene complexes of general formula [(η5-C5H5)2Mo(L)]Cl2 (L=6-mercaptopurine (2), 6-mercaptopurine ribose (3), 2-amino-6-mercaptopurine (4), 2-amino-6-mercaptopurine ribose (5)) have been prepared by reacting Cp2MoCl2 (1) with the corresponding thionucleobase/thionucleoside in a (2:1) THF/MeOH solvent mixture. The complexes have been characterized by spectroscopic methods (NMR, UV-Vis, IR and MS). 1H NMR spectroscopic data (DMSO-d6) on the complexes suggest a S-Mo-N(7) coordination by the thionucleobase/thionucleoside. In buffer solution NMR data suggest that the thionucleobase/thionucleoside remains coordinated to molybdenum probably through S(6) and assisted by either N(7) or N(1) atoms. Intermediate species such as [Cp2Mo(η1-L)(H2O)]2+/1+ where the L is acting as monodentate ligand are possible in solution. Electrochemical characterization has also been pursued by cyclic voltammetry in DMSO and buffer solution. In DMSO, the complexes including the molybdenocene dichloride exhibit reversible redox behavior. On the other hand, in buffer solution, the oxidation process is irreversible for all the species. 相似文献
13.
Jin-Ling Li Zi-Wei Gao Ping Sun Ling-Xiang Gao Wayne Tikkanen 《Inorganica chimica acta》2011,368(1):231-236
A method for the synthesis of titanocene (IV) aryl carboxylate complexes is presented in this paper. It is based on the fact that alcohol can catalyze the reaction between Cp2TiCl2 and aryl carboxylate ligands in the presence of sodium hydroxide (NaOH). The effects of the catalyst on the reaction system were studied and the possible reaction mechanism was proposed. This method was used to prepare a series of titanocene (IV) aryl carboxylate complexes and a macrocyclic titanocene (5,5′-dithiodisalicylato titanocene), whose structure was determined by X-ray diffraction analysis. 相似文献
14.
Mark Nieuwenhuyzen 《Inorganica chimica acta》2004,357(10):2870-2874
The benzaldehyde functionalized phosphine Ph2PC6H4CHO-2 underwent reaction with [(η5-C5Me5)MCl(μ-Cl)]2 (M=Rh, Ir) to form (η5-C5Me5)MCl2(κP-Ph2PC6H4CHO-2), which underwent activation of the aldehyde C-H bond to form (η5-C5Me5)MCl(κP,κC-Ph2PC6H4CO-2). Formally the reaction involves oxidative addition of C-H across the metal and reductive elimination of HCl. The structure of (η5-C5Me5)RhCl(κP,κC-Ph2PC6H4CO-2) has been determined by single-crystal X-ray diffraction. 相似文献
15.
Photoirradiation with a 150 W medium-pressure Hg lamp for 17 h in acetontrile as the solvent replaces the benzene ligand in the cationic complexes [(η6-C6H6)Ru(CH3CN)2(L)]2+ and [(η6-C6H6)Ru(CH3CN)(L2)]2+ (L=CH3CN, PPh3, L2=dppe, bipy) with acetonitrile. These replacements are equally clean to those reported before for analogous CpRu+ complexes. Crystal structures of the products obtained are included. 相似文献
16.
Kazuhiro Kawabata 《Inorganica chimica acta》2004,357(15):4373-4378
[Ir(η5-C5Me5)(C3S5)] [C3S52− = 4,5-disulfanyl-1,3-dithiole-2-thionate(2−)] was prepared by a reaction of [NMe4]2[C3S5] with [Ir(η5- C5Me5)Cl2]2 in ethanol. It was reacted with bromine to afford a paramagnetic species [IrBr(η5-C5Me5)(C3S5)] with the Ir-Br bond and in the one-electron-oxidized state, and a diamagnetic dinuclear species [IrBr(η5-C5Me5)(μ-C2S4)IrBr(η5-C5Me5)]. ESR spectra for the one-electron-oxidized species in solution are discussed. The X-ray crystal structural analysis for the latter complex revealed the geometry consisting of dinuclear IrBr(η5-C5Me5) moieties bridged by the C2S42− ligand. 相似文献
17.
Treatment of [Ru3(CO)9{P(C4H3S)3}(μ-dppm)] (1) [dppm = bis(diphenylphosphino)methane] with molecular oxygen in benzene at 60 °C affords oxo-capped [Ru3(CO)6(μ3-CO){P(C4H3S)3}(μ-dppm)(μ3-O)] (2), while with elemental sulfur and selenium related chalcogenide-capped clusters [Ru3(CO)6(μ3-CO){P(C4H3S)3}(μ-dppm)(μ3-E)] (3, E = S; 5, E = Se) and bis(chalcogenide) clusters [Ru3(CO)6{P(C4H3S)3}(μ-dppm)(μ3-E)2] (4, E = S; 6, E = Se) result. Reaction of 1 with H2S in refluxing THF affords the previously reported [(μ-H)2Ru3(CO)7(μ-dppm)(μ3-S)] (7) together with the new sulfido-capped dihydride [(μ-H)2Ru3(CO)6{P(C4H3S)3}(μ-dppm)(μ3-S)] (8). All new compounds have been characterized by spectroscopic data, and 2 and 8 by single-crystal X-ray diffraction analyses. Oxo-capped 2 consists of a triangular ruthenium framework capped on opposite sides by oxo and carbonyl groups, while 8 consists of a ruthenium triangle by a capping sulfido ligand and two inequivalent bridging hydride ligands. 相似文献
18.
Roberto Della Pergola Luigi Garlaschelli Carlo Manassero Donatella Strumolo Emanuela Grigiotti 《Inorganica chimica acta》2009,362(2):331-338
The reaction between [Fe2Ir2(CO)12]2− and diphenylacetylene in refluxing CH3CN yields the substituted cluster [Fe2Ir2(CO)10(PhC2Ph)]2− (1). In the crystals, the four metal atoms define a butterfly arrangement whose Ir-Ir hinge is parallel to the acetylenic C2 unit. The neutral triangular cluster [FeIr2(CO)9(PhC2Ph)] (2) is obtained by the treatment of 1 with acids at room temperature; in this 48 valence electrons species, the C-C and the Ir-Ir bonds are also parallel, in the coordination mode.The cluster [Fe2Rh(CO)10]− reacts with diphenylacetylene in refluxing THF yielding [Fe2Rh(CO)8(PhC2Ph)]− (3). In this 46 C.V.E.’s cluster, the C2 unit is perpendicular to the Fe-Fe edge, exemplifying the bonding mode. According to 13C NMR spectra, the structure of the three clusters is maintained in solution. Electrochemical investigations show that the one-electron oxidation of [Fe2Ir2(CO)10(L)]2− (L = 2CO, PhC2Ph) as well as the one-electron reduction of [Fe2Rh(CO)8(PhC2Ph)]− only generates the respective short lived products. 相似文献
19.
The reduction of ethanolic solutions of niobium pentachloride with zinc, followed by treatment with aqueous acids serves as a versatile entry into the aqueous solution chemistry of niobium. From the zinc-reduced solution, the major intermediate, Nb4(μ2-O)2(μ2-OC2H5)4Cl4(OC2H5)4(HOC2H5)4, was isolated and the crystal structure determined by X-ray crystallography. The complex crystallizes in the orthorhombic space group Pccn, with Z=4, a=21.0105(9), b=11.0387(5), c=19.1389(8), V=4438.9(3) Å3, Mr=1090.19,R1=0.0327 and wR2=0.0876. The structure revealed a centrosymmetric tetrameric Nb(IV) complex, consisting of a pair of edge-sharing bi-octahedral Nb2(μ2-OC2H5)4Cl2(OC2H5)2(HOC2H5)2 units that are joined by two axial oxo ligands. The Nb-Nb distance of 2.7458(3) Å is consistent with a single metal-metal bond. 相似文献
20.
The cationic carbyne complex [Cp(CO)2MnCC6H5]BBr4 (1) reacts with PPN[Rh(CO)4] (2) to give the title cluster [(μ3-CC6H5)(μ-CC6H5) Rh2Mn2Cp2(μ-CO)3(CO)3] (3) whose structure has been determined by X-ray diffraction. The electrochemical properties of 3 have been investigated using cyclic voltammetric method. At 60 °C and 2.0 MPa of initial total CO/H2 (1:1) pressure, the catalytic activity of 3 towards hydroformylation of styrene has also been checked. 相似文献