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1.
The reaction between [7,8-Ph2-7,8-nido-C2B9H9]2− and [(η-C7H7)Mo(MeCN)3]+ affords five products. Four have been isolated and shown to be structural isomers of (η-C7H7)MoPh2C2B9H9. Compound 1 has a pseudocloso structure. In solution it gives way to the non-icosahedral compound 2 which in turn rearranges into the “1,2 → 1,7” C-atom isomerised compound 5 having a 2,1,8-MoC2B9 structure. A further “1,2 → 1,7” C-atom isomerised species, compound 4, is also isolated but has a 1,2,4-MoC2B9 architecture. Compound 4 forms via an intermediate 3, which is too unstable to characterise. Structurally the sequence of compounds 1, 2 and 5 maps well onto the sequential diamond-square-diamond isomerisation mechanism of 1,2-closo-C2B10H12 into 1,7-closo-C2B10H12 proposed by Wales. An alternative pathway from the notional first product of the metallation, 1,2-Ph2-3-(η-C7H7)-3,1,2-closo-MoC2B9H9, is required to rationalise the intermediate compound 3 and, from it, compound 4.  相似文献   

2.
Three group 10 complexes containing nido-carborane diphosphine, [NiCl(PPh3){7,8-(PPh2)2-7,8-C2B9H10}] (1), [PdCl(PPh3){7,8-(PPh2)2-7,8-C2B9H10}] · 1.25CH2Cl2 (2) and [PtCl(PPh3){7,8-(PPh2)2-7,8-C2B9H10}] · 2.5CH2Cl2 (3) have been synthesized by the reactions of [M(PPh3)2Cl2] (M = Ni, Pd, Pt) with closo carborane diphosphine 1,2-(PPh2)2-1,2-C2B10H10 in ethanol. For complex 3, it could also be obtained under solvothermal condition. All three complexes were characterized by elemental analysis, FT-IR, 1H and 13C NMR spectroscopy and X-ray structure determination. Single crystal structures show that their structures are similar to each other. In each complex, the nido [7,8-(PPh2)2-7,8-C2B9H10], which resulted from the degradation of the initial closo ligand 1,2-(PPh2)2-1,2-C2B10H10 during the reaction process, was coordinated bidentately through the P atoms to M(II) ion, and this resulted in a stable five-membered chelating ring between the bis-diphosphine ligand and the metal. The coordination mode of the metal can be described as a slightly distorted square-planar, in which the remaining two positions were occupied by one Cl and one PPh3 group.  相似文献   

3.
The reaction between [5-I-7,8-Ph2-7,8-nido-C2B9H8]2− and NiCl2(dppe) affords 1,2-Ph2-4,4-dppe-12-I-4,1,2-closo-NiC2B9H8 (1) and 1,8-Ph2-2,2-dppe-10-I-2,1,8-closo-NiC2B9H8 (2). Reaction between the same carborane ligand and cis-PtCl2(PMe2Ph)2 yields three species, 1,8-Ph2-2,2-(PMe2Ph)2-10-I-2,1,8-closo-PtC2B9H8 (3), 1,8-Ph2-2,2-(PMe2Ph)2-12-I-2,1,8-closo-PtC2B9H8 (4), and 1,8-Ph2-2,2-(PMe2Ph)2-7-I-2,1,8-closo-PtC2B9H8 (5). Compounds 1-5 have been characterised spectroscopically and crystallographically. The 4,1,2-MC2B9 architecture of 1 constitutes a “1,2 → 1,2” cage C atom isomerisation, and the 2,1,8-MC2B9 architectures of 2-5 a 1,2 → 1,7 cage C atom isomerisation, relative to the presumed first product of the metallations, 1,2-Ph2-3,3-L2-9-I-3,1,2-closo-MC2B9H8 [M = Ni, L2 = dppe; M = Pt, L2 = (PMe2Ph)2]. The location of the (iodide) labelled boron vertex in the products allows speculation as to the mechanism of these isomerisations and the possible involvement of triangle face rotation is discussed.  相似文献   

4.
The meta-diaminoaryl ferrocenes Fc-NCN-H (3) and Fc-CC-NCN-H (5) (Fc = (η5-C5H5)(η5-C5H4)Fe, NCN-H = C6H3(CH2NMe2)2-3,5) can be used as precursors in the preparation of heterobimetallic transition metal complexes of structural type Fc-NCN-MX (NCN = [C6H2(CH2NMe2)2-2,6]; MX = PdCl (7), PtCl (8), PtI (9)) and Fc-CC-NCN-MX (MX = PdCl (11), PdI (12), PtCl (13)), respectively. They are accessible by applying different synthesis procedures, including oxidative addition and metallation-transmetallation processes.Cyclovoltammetric studies show that the ferrocene moieties in 3, 5, 7-9 and 11-13 can reversibly be oxidised. The potential of the Fe(II)/Fe(III) redox couple decreases with increasing electron density at the NCN pincer unit. The use of 8 as a possible (electro)chemical sensor in the detection of SO2 is discussed as well.The solid-state structures of 8 and 13 are reported. The crystals of 8 contain two molecules of 8 in the asymmetric unit. The plane of the C6H2 moiety is with 27.2(3)° and 38.2(3)° tilted towards the C5H4 entity, while in 13 an angle of 45.9(3)° can be found. The d8-electron configured platinum atoms possess a somewhat distorted square-planar surrounding, setup by two Me2NCH2ortho-substituents, the NCN Cipso carbon atom and the chloride ligand.  相似文献   

5.
Metal-sulfur complex fragments, to which small molecules like N2, N2H2, N2H4, NH3, or CO can bind, are desirable model compounds concerning enzymatic N2 fixation.This paper reports on the effects of the phosphane co-ligand on formation and reactivity of [Ru(L)(PR3)(`N2Me2S2')] [`N2Me2S2'2−=1,2-ethanediamine-N,N-dimethyl-N,N-bis(2-benzenethiolate)(2−)] complexes with nitrogenase relevant ligands, especially N2, N2H4, NH3, and CO.Treatment of [Ru(NCCH3)4Cl2] with Li2`N2Me2S2', excessive LiOMe, bulky PPh3 or PCy3, respectively, led to the formation of two series of [Ru(L)(PR3)(`N2Me2S2')] complexes [for R=Ph: 1b, 1c (L=NCCH3), 6b (L=N2H4), 7b (L=N2), 8b1-3 (L=CO), 9b (L=NH3); for R=Cy: 1a (L=NCCH3), 6a (L=N2H4), 7a (L=N2), 8a (L=CO), 9a (L=NH3)]. While the use of PPh3 (θ=145°) yielded cis,trans and cis,cis isomers of [Ru(NCCH3)(PPh3)(`N2Me2S2')] (1b, 1c), no isomer formation was observed with the bulkier phosphane PCy3 (θ=170°). Sterically less demanding phosphanes (θ=118-132°) afforded bisphosphane complexes [Ru(PR3)2(`N2Me2S2')] [2d (R=Me), 2e (R=Et), 2f (R=nPr), and 2g (R=nBu)], which were practically inert and could only be converted in two cases and under drastic reaction conditions into the CO complexes [Ru(CO)(PR3)(`N2Me2S2')] [4e (R=Et), 4f (R=nPr)]. The chelating bidentate phosphane dppe (bisdiphenylphosphanoethane) yielded exclusively the mononuclear complex [Ru(dppe)(`N2Me2S2')] (3).  相似文献   

6.
Photolysis of the molybdaborane [(η5-C5H5)(η51-C5H4)-arachno-2-MoB4H7] (1) in benzene-d6 gives ca. 60% conversion to the compound [(η5-C5H5)(η51-C5H4)-nido-2-MoB4H5] (2). Compound 2 could not be isolated as a solid and is thermally unstable at 20 °C in solution with a half-life of 3-4 h. Repeated photolysis and thermolysis of 1 in the presence of BH3 · thf gives a low yield of the known metallacarbaborane [(η5-C5H5)(η23-C3H3)-closo-1-MoC2B9H9] (3) suggesting that 3 is formed from 1 via 2. Reaction of 1 with PEt3 gives initially [(η5-C5H5)(η51-C5H4)-arachno-2-MoHB4H4PEt3] (4). Longer reaction times (>10 min, 20 °C) give in addition [(η5-C5H5)(η51-C5H4)-arachno-1-MoHB3H3PEt3] (5). Both 4 and 5 are unstable in solution or the solid state decomposing to the molybdacarbaborane [(η5-C5H5)(η32- C3H3)-nido-1-MoC2B3H5] (6), [Mo(η-C5H5)2H2] and BH3 · PEt3. Compound 1 is deprotonated cleanly by KH in thf at the Mo-H-B bridging proton to give (7).  相似文献   

7.
The mechanism for the preparation of Me2Si(C5Me4)2Cr, 1, from CrCl2(THF)x and Me2Si(C5Me4)2Li2 was investigated and - in contrast to earlier claims - no evidence was found for the participation of an auxiliary ligand. The formation and stability of 1 is attributed to the combination of correct reaction conditions and a highly substituted ligand framework. Reactions with other ligands under identical conditions did not lead to the formation of ansa-chromocenes. Reaction with H4C2Ind2Li2 afforded the η3-Ind bridged dimer {H4C25-Ind)(μ-,η3-Ind)Cr}2, 9. Complex 1 does not coordinate PPh3 or carbenes, but from reaction with two equivalents of xylyl isocyanide the CH-activated complex Me2Si(C5Me4)(η3-C5Me3(H)(CH2)Cr(CNC6MeH3)2, 7, was obtained. Complexes 7 and 9 were characterised by X-ray crystallography.  相似文献   

8.
The reaction of [60]fullerene with Me3SiCH2MgCl in 1,2-Cl2C6H4/THF (1/1) under dry air afforded a bis-alkyl adduct, C60(CH2SiMe3)2 (1), in 54% yield. Treatment of 1 with Me3SiCH2MgCl in THF under argon then afforded a trialkyl[60]fullerene, C60(CH2SiMe3)3H (2), in 37% yield. Further treatment of 2 with KOtBu gave a potassium salt, [K(thf)n][C60(CH2SiMe3)3] (3), which was then converted to a Cs-symmetric Rh(I) complex, Rh[η5-C60(CH2SiMe3)3](1,5-cyclooctadiene) (4), in 91% yield.  相似文献   

9.
A dissymmetrical double Schiff base Cu(II) mononuclear complex: CuHL (1) (where H3L is N-3-carboxylsalicylidene-N-salicylaldehyde-1,2-diaminoethane) and two trinuclear complexes: [CuL(H2O)CoCuL] · H2O · CH3OH (2) and [(CuL)2Ni] · 2H2O (3) have been synthesized and characterized by means of elemental analyses, IR and electronic spectra. The crystal structures of two heterotrinucler complexes were determined by X-ray analysis. Each dissymmetrical cell unit of the complex 2 contains two heterotrinucler neutral molecules. In each neutral molecule, the central Co2+ ion is located at the site of O6 with a distorted octahedral geometry and one terminal Cu2+ ion at the four-coordination site of N2O2, but the other one at the square-pyramidal environment of N2O3. Each dissymmetrical unit of the complex 3 contains a heterotrinucler neutral molecule, whose structure is similar to that of 2 except two terminal Cu2+ ions both at the inner site of N2O2. The magnetic properties of two heterotrinucler complexes have been determined in the temperature range of 5-300 K, which indicate that the interaction between the central Co2+ ion or Ni2+ ion and the outer Cu2+ ions is antiferromagnetic. The exchange integrals are equal to −26.2 cm−1 for 2 and −50.6 cm−1 for 3.  相似文献   

10.
The cooperative effect of the camphor imine ligand (YNC10H14O) in the cyclization of 5-hexyn-1-ol and 4-pentyn-1-ol promoted by complexes trans-[MCl2(YNC10H14O)2] (M = Pd, Y = NH2, NHMe, NMe2, OH, Ph; Pt, Y = NH2, NHMe, NMe2) is established from a direct relation between the constants calculated for conversion of 5-hexyn-1-ol (A) into 2-methyl-2-pent-4-ynyloxy-tetrahydropyran (B) and 4-pentyn-1-ol (C) into 2-methyl-2-pent-4-ynyloxy-tetrahydrofuran (D) and the basic character of the camphor imine substituent (Y). In the catalytic process acid-base interactions between the alkynol and the coordinated camphor imine are supported by the structural characterization of [PdCl4][Me2NHNC10H14O]2.  相似文献   

11.
1,2,4-Trimethyl-cyclohexadiene reacts with RuCl3 · nH2O in refluxing ethanol to afford quantitatively [RuCl2(1,2,4-C6H3Me3)]2 (1), the coordination of 1,2,4-trimethylbenzene to the ruthenium atom introducing planar chirality at the η6-arene ligand. The dinuclear complex 1 reacts with two equivalents of triphenylphosphine (PPh3) to give quantitatively, as a racemic mixture of enantiomers, [RuCl2(1,2,4-C6H3Me3)(PPh3)] (2), the structure of which has been determined by a single-crystal X-ray structure analysis of (rac)-2. Similarly, 1 reacts with two equivalents of the enantiopure phosphine (1S,2S,5R)-(+)-neomenthyldiphenylphosphine (nmdpp) to afford in good yield [RuCl2(1,2,4-C6H3Me3)(nmdpp)] (3) as a mixture of diastereoisomers, from which the isomer 3a was isolated by crystallisation. A single-crystal X-ray structure analysis of 3a allowed the determination of the absolute configuration at the planar chiral η6-arene moiety. Finally, complex 1 reacts with one equivalent of the diphosphine ligand 1,1-bis(diphenylphosphino)ferrocene (dppfc) to give the heteronuclear complex [RuCl2(1,2,4-C6H3Me3) (dppfc)RuCl2(1,2,4-C6H3Me3)] (4). All complexes were fully characterised by elemental analysis, mass spectrometry, NMR and IR spectroscopies.  相似文献   

12.
New C-ansa-zirconocene complexes containing methoxythiophenolate and mercaptophenolate ligands have been synthesized and characterized. The reaction of (HSC6H4-n-OMe) (n = 2, 3 or 4) with [Zr{(t-Bu)HC(η5-C5Me4)(η5-C5H4)}Me2] (1) led to the formation of monosubstituted complexes [Zr{(t-Bu)HC(η5-C5Me4)(η5-C5H4)}Me(κ,S-SC6H4-n-OMe)] (= 2 (2); = 3 (3)) and the disubstituted complex [Zr{(t-Bu)HC(η5-C5Me4)(η5-C5H4)}(κ,S-SC6H4-4-OMe)2] (4). The complexes [Zr{(R)HC(η5-C5Me4)(η5-C5H4)}(κ,O-OC6H4-4-SH)2] (R = t-Bu (6); R = CH2CHCH2 (7)) and [Zr(η5-C5H4)2(OC6H4-n-SH)2] (= 3 (9); = 4 (10)) have been synthesized using the corresponding dimethyl zirconocene and mercaptophenol. However, the reaction of [Zr{(t-Bu)HC(η5-C5Me4)(η5-C5H4)}Cl2] (11) with 4-mercaptophenol in the presence of NEt3 led to the formation of the first example of a homoleptic six-coordinate mercaptophenolate complex of zirconium, namely [HNEt3]2[Zr(κ,O-OC6H4-4-SH)6] (12). Complex 12 can be obtained in higher yield by the reaction of ZrCl4 with six equivalents of 4-mercaptophenol and NEt3. The reaction of 12 with [Zr(η5-C5H4)2Cl2] gave the unexpected disubstituted complex [Zr(η5-C5H4)2(OC6H4-4-SH)2] (10). The molecular structures of 4 and 12 have been determined by single-crystal X-ray diffraction studies.  相似文献   

13.
Novel bipyridine-type linking ligands L1 ((4-py)-CHN-C10H6-NCH-(4-py)) and L2 ((3-py)-CHN-C10H6-NCH-(3-py)), a pair of isomers due to possessing different pairs of terminal pyridyl groups, were prepared by the Schiff-base condensation. In ligand L1, the N?N separation between the terminal pyridyl groups is 16.0 Å, with their nitrogen donor atoms at the para positions (4,4′). The corresponding N?N separation in ligand L2 is 14.2 Å, with the nitrogen donor atoms at the meta positions (3,3′). 1-D zigzag-chain coordination polymers [Zn(L1)(NO3)2] (1) and [Zn(L2)(NO3)2] (2) were prepared by reactions of Zn(NO3)2 · 6H2O with ligands L1 and L2, respectively, by solution diffusion. Polymer 3, [Cd(L1)1.5(NO3)2], prepared from Cd(NO3)2 · 4H2O and L1, exhibits a 1-D ladder structure, whose repeating ladder unit consists of four Cd metals and four L1 ligands to create a large 76-membered ring with dimensions of 20.8 × 20.8 Å. All products were structurally characterized by X-ray diffraction.  相似文献   

14.
《Inorganica chimica acta》2004,357(10):3119-3123
Fused double-cluster [(η5-C5Me5)IrB18H18(PH2Ph)] (8), from syn-[(η5-C5Me5)IrB18H20] (1) and PH2Ph, retains the three-atoms-in-common cluster fusion intimacy of 1, in contrast to [(η5-C5Me5)HIrB18H19(PHPh2)] (6), from PHPh2 with 1, which exhibits an opening to a two atoms-in-common cluster fusion intimacy. Compound 8 forms via spontaneous dihydrogen loss from its precursor [(η5-C5Me5)HIrB18H19(PH2Ph)] (7), which has two-atoms-in-common cluster-fusion intimacy and is structurally analogous to 6.  相似文献   

15.
Thiocarbonate ruthenium complexes of the form CpRu(L)(L′)SCO2R (L = L′ = PPh3 (1), 1/2 dppe (2), L = PPh3, L′ = CO (3); R = Et (a), Bun (b), C6H5 (c), 4-C6H4NO2 (d)) have been synthesized by the reaction of the corresponding sulfhydryl complexes, CpRu(L)(L′)SH, with chloroformates, ROCOCl, at low temperature. The bis(triphenylphosphine) complexes 1 can be converted to 3 under CO atmosphere. The crystal structures of CpRu(PPh3)2SCO2Bun (1b), CpRu(dppe)SCO2Bun (2b), and CpRu(PPh3)(CO)SCO2Bun (3b) are reported.  相似文献   

16.
Reaction of [CuIIL⊂(H2O)] (H2L = N,N′-ethylenebis(3-ethoxysalicylaldimine)) with nickel(II) perchlorate in 1:1 ratio in acetone produces the trinuclear compound [(CuIIL)2NiII(H2O)2](ClO4)2 (1). On the other hand, on changing the solvent from acetone to methanol, reaction of the same reactants in same ratio produces the pentametallic compound [(CuIIL)2NiII(H2O)2](ClO4)2·2[CuIIL⊂(H2O)]·2MeOH (2A), which loses solvated methanol molecules immediately after its isolation to form [(CuIIL)2NiII(H2O)2](ClO4)2·2[CuIIL⊂(H2O)] (2B). Clearly, formation of 1 versus 2A and 2B is solvent dependent. Crystal structures of 1 and 2A have been determined. Interestingly, compound 2A is a [3 × 1 + 1 × 2] cocrystal. The cryomagnetic profiles of 1 and 2B indicate that the two pairs of copper(II)···nickel(II) ions in the trinuclear cores in both the complexes are coupled by almost identical moderate antiferromagnetic interaction (J = −22.8 cm−1 for 1 and −26.0 cm−1 for 2B).  相似文献   

17.
A trinuclear copper(II) complex, [Cu3(2,5-pydc)2(Me5dien)2(BF4)2(H2O)2] · H2O 1, has been constructed from 2,5-pyridine-dicarboxylato bridges (2,5-pydc2−) and N,N,N′,N″,N″-pentamethyl-diethylenetriamine (Me5dien) acting as a blocking ligand. The copper ions, within the centrosymmetric trinuclear cations, are connected by two 2,5-pydc2− bridges, with an intramolecular Cu···Cu separation of 8.432 Å. The central copper ion exhibits an elongated octahedral geometry, with semicoordinated ions, while the terminal ones are pentacoordinated (distorted square-pyramidal geometry). The cryomagnetic investigation of 1 reveals an antiferromagnetic coupling of the copper(II) ions (J = −5.9 cm−1, H = −JSCu1SCu2 − JSCu2SCu1a).  相似文献   

18.
The reactivity of the iron selenide complex (μ-Se)[CpFe(CO)2]2 toward chloroformates, ROCOCl, has been studied and the products CpFe(CO)2SeCO2R [R=Me (1), Et (2), iso-Bu (3), Ph (4), 2-C6H4Cl (5), 4-C6H4Cl (6), and 4-C6H4NO2 (7)] have been obtained. The novel complexes, 1-7, have been characterized by elemental analyses, IR and 1H NMR spectroscopy. The solid state structure of CpFe(CO)2SeCO2Et, 2, was determined by an X-ray crystal structure analysis.  相似文献   

19.
The cytotoxic effect of vanadocene dichloride (Cp2VCl2, 1) and its ring-substituted, (η5-C5H4Me)2VCl2 (2), (η5-C5Me5)2VCl2 (3), (η5-C5H4R)2VCl2 (4: R = MeOCH2CH2-, 5: R = 2-MeOC6H4CH2-, 6: R = 4-MeOC6H4CH2-) and ansa-bridged analogs Me2C(η5-C5H4)2VCl2 (7) and Me4C25-C5H4)2VCl2 (8) was investigated. Synthesis of two new methoxy-functionalized compounds (4 and 5) is described. They were characterized by spectroscopic methods and X-ray diffraction analysis. The cytotoxicity studies were performed with leukemic cells MOLT-4.  相似文献   

20.
Single crystals of three derivatives of the structurally still incompletely characterized coordination polymer [(Me3Sn)4Ru(CN)6] 1b have been prepared and subjected to crystallographic studies: [1b · 4H2O]=2b forms stacks of puckered 2[Ru{μ-CNSn(Me3)NC}2] sheets interlinked by hydrogen bonds in making use of two additional CNSn(Me3)OH2 ligands and quasi-zeolitic water. Mild drying of 2b leads to the “missing link” between 1b and 2b, [1b · 2H2O], 3b. The structure of [1b · 2tp] (tp=4-thiopyridone) consists of a three-dimensional, negatively charged host framework comprising (via Sn-S bonds) one “aromatic” thione linkage and a [Me3Sn · tp]+guest ion involving a more zwitterionic form of tp. Slow uptake of Me3SnCl from the gas phase by an aqueous solution of K4[Ru(CN)6] and tp afforded the novel assembly [1b · 2H2O · 0.8pms · 0.2pds] (pms/pds=4,4-dipyridylmono-/disulfide), the supramolecular architecture of which resembles that of 2b. Bridging pms or pds molecules occupy equivalent interlayer sites, and the pms/pds ratio is likely to vary. At least three further assemblies containing again 1b and either tp or pds/pms have likewise been isolated, however, not as single crystals.  相似文献   

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