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1.
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   

2.
[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   

3.
Hydrothermal reaction of copper(II) chloride with 2-hydroxypyrimidine generated double salt of [Cu2Cl(μ4-pymo)] (1) (Hpymo = hydroxylpyrimidine) while hydrothermal treatment of CuCl2, NaN3 and acetonitrile resulted in double salt of [Cu2(mtta)Cl] (2) (Hmtta = 5-methyltetrazole) in which in situ [2 + 3] cycloaddition reactions of acetonitrile with azide formed mtta ligand. X-ray single crystal structural analyses revealed that 1 shows a two-dimensional layer formed by fusion of one-dimensional structural motifs. The two-dimensional layers in 1 are held together by C-H?Cl hydrogen bonds to form three-dimensional supramolecular array. Compound 2 has a three-dimensional framework constructed from ribbons and [Cu8Cl4]4+ units. Uncommon coordination modes of μ4-1,2κO:3κN:4κN′ pymo and μ4-Cl (Cl at the apex of a Cu4Cl square pyramid) in 1 and μ41111 mtta in 2 were also observed. The short Cu(I)?Cu(I) distances were found in 1 and 2, indicating the existence of Cu(I)?Cu(I) interactions.  相似文献   

4.
The ansa-titanocene complexes, [Ti{Me2Si(η5-C5Me4)(η5-C5H3R)}Cl2] (R = Me (5), iPr (6), tBu (7), SiMe3 (8)), were obtained from the reaction of Li2{Me2Si(C5Me4)(C5H3R)} (R = Me (1), iPr (2), tBu (3), SiMe3 (4)) with [TiCl4(THF)2], respectively. Compounds 5-8 have been tested as catalysts in the polymerization of ethylene and compared with the ansa-titanocene complexes [Ti{Me2Si(η5-C5H4)2}Cl2] and [Ti{Me2Si(η5-C5Me4)(η5-C5H4)}Cl2]. The resulting polyethylene showed molecular weights of about 200 000 g mol−1 and polydispersity values of approximately 3. In addition, the molecular structure of 6 has been determined by single crystal X-ray diffraction studies.  相似文献   

5.
The preparation of a series of 1,2-phenylenedioxoborylcyclopentadienyl-metal complexes is described. These are of formula [M{η5-C5H4(BX)}Cl3] [M = Ti and X = CAT (2a), CATt (2b) or CATtt (2c); X = CATtt and M = Zr (4a) or Hf (4b)], [M{η5-C5H4(BX)}2Cl2] [M = Zr, X = CAT (3a) or CATt (3c); or M = Hf, X = CAT (3b) or CATt (3d)], [M{(μ-η5-C5H3BCAT)2 SiMe2}Cl2] [M = Zr (5a) or Hf (5b)], [M{η5-C5H3(BCAT)2}Cl3] [M = Zr (6a) or Hf (6b)], [M{η5-C5H4BCAT}3(THF)] [M = La (7a), Ce (7b) or Yb (7c)], [Sn{η5-C5 H4(BCATt)}Cl](8) and [Fe{η5-C5H4(BCATt)}2] (9). The abbreviations refer to BO2C6H4-1,2 (BCAT) and the 4-But (BCATt) and the (BCATtt) analogues. The compounds 2a-9 have been characterised by microanalysis, multinuclear NMR and mass spectra. The single crystal X-ray structure of the lanthanum compound 7a is presented.  相似文献   

6.
Three novel coordination polymers [Ca(5-OH-BDC)(H2O)3] · H2O (1), [Sr(5-OH-BDC)(H2O)4] · H2O (2) and [Ba(5-OH-BDC)(H2O)3] (3) were obtained by self-assembly of the corresponding alkaline earth metal chlorate with a ligand, 5-hydroxyisophthalic acid (5-OH-H2BDC), and their structures were determined by X-ray crystallography. The results revealed that complexes 1, 2 and 3 have two-dimensional network with (6, 3) topology observed in the bc plane. Moreover, the two-dimensional layers can be assembled into three-dimensional supramolecular architectures via intermolecular hydrogen bonds. The two carboxylate groups of 5-OH-BDC2− ligand adopt the same coordination mode in complex 1 as that in 2: a μ3-η2:η1 mode and a chelated mode while in complex 3 they coordinate to Ba(II) ions in a μ3-η2:η1 mode and a monodentate mode, which is not observed in previous reports. The constant-volume combustion energies, ΔcU, of these complexes were determined by a precise rotating-bomb calorimeter at 298.15 K, then their standard enthalpies of combustion, , and the standard enthalpies of formation, , have been calculated.  相似文献   

7.
The combination of transition metal ions with mixed ligands resulted in the formation of three new coordination polymers, {[Co(C4H4O5)(bpe)(H2O)2] · (0.5bpe)(H2O)}n (1), {[Cu(C4H4O6)(bipy)] · 5H2O}n (2) and {[Cu(C4H4O5)(bpa)] · 2.5H2O}n (3) (, , bpe = 1,2-bis(4-pyridyl)ethene, bipy = 2,2′-bipyridine, bpa = 1,2-bis(4-pyridyl)ethane), which were prepared under solvothermal conditions and characterized by single-crystal X-ray diffraction. 1 and 2 feature 1D chain structures. Interestingly, each pair of chains recognizes each other through aromatic π-π stacking interactions, generating a zipper-like double-stranded chain in 2. Compound 3 shows 2D 63 topology framework with a rectangle-like grid.  相似文献   

8.
The 2-methallyl complex [(η5-C9H7)Ru(η3-2-MeC3H4)(PPh3)] (3), prepared from [(η5-C9H7)Ru(PPh3)2Cl] (2) and 2-MeC3H4MgCl, reacts with HX (X = Cl, CF3CO2) in the presence of ethene to give the chiral-at-metal compounds [(η5-C9H7)Ru(C2H4)(PPh3)X] (4, 5) in nearly quantitative yields. Treatment of 2 with AgPF6 and ethene affords [(η5-C9H7)Ru(C2H4)(PPh3)2]PF6 (6), which reacts with acetone to give the substitution product [(η5-C9H7)Ru(OCMe2)(PPh3)2]PF6 (7). The molecular structure of 7 has been determined crystallographically. Whereas treatment of 4 with CH(CO2Et)N2 yields the olefin complex [(η5-C9H7)Ru{η2-(Z)-C2H2(CO2Et)2}(PPh3)Cl] (8), the reactions of 4 and 5 with Ph2CN2, PhCHN2 and (Me3Si)CHN2 lead to the formation of the carbeneruthenium(II) derivatives [(η5-C9H7)Ru(CRR′)(PPh3)Cl] (9-11) and [(η5-C9H7)Ru(CRR′)(PPh3)(κ1-O2CCF3)] (12-14), respectively. Treatment of 9 (R = R′ = Ph), 10 (R = H, R′ = Ph) and 11 (R = H, R′ = SiMe3) with MeLi produces the hydrido(olefin) complexes [(η5-C9H7)RuH(η2-CH2CPh2)(PPh3)] (15), [(η5-C9H7)RuH(η2-CH2CHPh)(PPh3)] (18a,b) and [(η5-C9H7)RuH(η2-CH2CHSiMe3)(PPh3)] (19) via C-C coupling and β-hydride shift. The analogous reactions of 11 with PhLi gives the η3-benzyl compound [(η5-C9H7)Ru{η3-(Me3Si)CHC6H5}(PPh3)] (20). The η3-allyl complex [(η5-C9H7)Ru(η3-1-PhC3H4)(PPh3)] (17) was prepared from 10 and CH2CHMgBr by nucleophilic attack.  相似文献   

9.
The reaction of FcCOCl (Fc = (C5H5)Fe(C5H4)) with benzimidazole or imidazole in 1:1 ratio gives the ferrocenyl derivatives FcCO(benzim) (L1) or FcCO(im) (L2), respectively. Two molecules of L1 or L2 can replace two nitrile ligands in [Mo(η3-C3H5)(CO)2(CH3CN)2Br] or [Mo(η3- C5H5O)(CO)2(CH3CN)2Br] leading to the new trinuclear complexes [Mo(η3-C3H5)(CO)2(L)2Br] (C1 for L = L1; C3 for L = L2) and [Mo(η3-C5H5O)(CO)2(L)2Br] (C2 for L = L1; C4 for L = L2) with L1 and L2 acting as N-monodentade ligands. L1, L2 and C2 were characterized by X-ray diffraction studies. [Mo(η3-C5H5O)(CO)2(L1)2Br] was shown to be a trinuclear species, with the two L1 molecules occupying one equatorial and one axial position in the coordination sphere of Mo(II). Cyclic voltammetric studies were performed for the two ligands L1 and L2, as well as for their molybdenum complexes, and kinetic and thermodynamic data for the corresponding redox processes obtained. In agreement with the nature of the frontier orbitals obtained from DFT calculations, L1 and L2 exhibit one oxidation process at the Fe(II) center, while C1, C3, and C4 display another oxidation wave at lower potentials, associated with the oxidation of Mo(II).  相似文献   

10.
Coordination polymers Cu(l-Pro)(ClO4)(H2O)2 (1) and Cu3(Gly)4(H2O)2(NO3)2 (2) were synthesized and characterized structurally. Compound 1 possesses the structure of 1D chain, where Cu(II) ions are linked by carboxyl-group in syn-anti conformation in equatorial-equatorial mode. Compound 2 is polymeric chain, consisting from trinuclear blocks Cu3(Gly)4(H2O)22+. In each of these units Cu(II) ions are linked by carboxyl-group in the same way as in 1, while trinuclear units Cu3(Gly)4(H2O)22+ are linked by NO3 ions, acting as the bridges between Cu(II) ions of neighboring trinuclear units. Circular dichroism properties of 1 were studied in solid state and solution. Magnetic measurements revealed that there were ferromagnetic exchange interactions between Cu(II) ions in 1 (J = +1.22(1) cm-1 for Hamiltonian ) and 2 (J = +1.17(2) cm-1 for Hamiltonian ).  相似文献   

11.
The reaction of the racemic chiral methyl complex (η5-C5H5)Re(NO)(PPh3)(CH3) (1) with CF3SO3H and then NH2CH2C6H5 gives [(η5-C5H5)Re(NO)(PPh3)(NH2CH2C6H5)]+ ([4a-H]+; 73%), and deprotonation with t-BuOK affords the amido complex (η5-C5H5)Re(NO)(PPh3)(NHCH2C6H5) (76%). Reactions of 1 with Ph3C+ X and then primary or secondary amines give [(η5-C5H5)Re(NO)(PPh3)(CH2NHRR′)]+ X ([6-H]+ X; R/R′/X = a, H/NH2CH2C6H5/BF4; a′, H/NH2CH2C6H5/PF6; b, H/NH2CH2(CH2)2CH3/PF6; c, H/(S)-NH2CH(CH3)C6H5/BF4); d, CH2CH3/CH2CH3/PF6; e, CH2(CH2)2CH3/CH2(CH2)2CH3/PF6; f, CH2C6H5/CH2C6H5/PF6; g, -CH2(CH2)2CH2-/PF6; h, -CH2(CH2)3CH2-/PF6; i, CH3/CH2CH2OH/PF6 (62-99%). Deprotonations with t-BuOK afford the amines (η5-C5H5)Re(NO)(PPh3)(CH2NRR′) (6a-i; 99-40%), which are more stable and isolated in analytically pure form when R ≠ H. Enantiopure 1 is used to prepare (RReSC)-[6c-H]+, (RReSC)-6c, (S)-[6g-H]+, and (S)-6g. The crystal structures of [4a-H]+, a previously prepared NH2CH2Si(CH3)3 analog, [6a′,d,f,h-H]+, (RReSC)-6c, and 6f are determined and analyzed in detail, particularly with respect to cation/anion hydrogen bonding and conformation. In contrast to analogous rhenium containing phosphines, 6a-i show poor activities in reactions that are catalyzed by organic amines.  相似文献   

12.
Four one-dimensional coordination polymers, [Ln(H2O)4(HTDA)(H2TDA)] · H2O [Ln = Sm (1) and Eu (2)]; (H3TDA = 1H-[1,2,3]-triazole-4,5-dicarboxylic acid), [Ln(H2O)4(HTDA)] · (H2TDA) · H2O [Ln = Tb (3) and Dy (4)] were prepared and characterized by IR, elemental analysis, PXRD and single-crystal X-ray diffraction. The powder and single-crystal X-ray crystallographic studies of 1-4 reveal that all compounds are one-dimensional zigzag chain structures. Luminescent studies reveal that they are potential luminescent materials. Moreover, in solution, the emission intensity of 2 increases upon the addition of Ca2+ ions, while introduction of other metal ions leads to either unchanged or decreased intensity, which indicates that 2 may be applied as a promising Ca2+-ion-selective luminescent probe. The basic magnetic properties of 1-4 were also studied.  相似文献   

13.
One-dimensional lanthanide-ferrocenesuccinate polymeric complexes [M(η2-FcCOC2H4COO)(μ22-FcCOC2H4COO)2(H2O)2]n (Fc = (η5-C5H4)Fe(η5-C5H4), M = Pr, 1; Ce, 2; La, 3) have been synthesized and structurally characterized by single-crystal X-ray crystallography. The three polymers are isomorphous, in which each Ln(III) ion is 10-coordinated and connects with two water molecules and eight oxygen atoms from ferrocenesuccinate units in two kinds of coordination modes: bidentate-chelating mode and tridentate-bridging mode. The variable-temperature magnetic susceptibility in the temperature range 5-300 K for 1 and 2 shows that both of them display weak antiferromagnetic interaction. In addition, the redox and fluorescent properties have been investigated. The redox properties are different from the previous results of transition metal compounds containing ferrocenyl systems. Compared with sodium ferrocenesuccinate, polymers 1 and 3, the fluorescent intensities of 2 are markedly enhanced in the solid state.  相似文献   

14.
Three new coordination polymers based on IB metal thiocyanates, [CuII(NCS)2(DMSO)4(meso-dpb)]n (1), (2), [CuI(NCS)(pia)]n (3) (dpb = 2,3-di(4-pyridyl)-2,3-butanediol, bpp = 1,3-bis(4-pyridyl)propane, pia = N,N′-(1,2-phenylene)diisonicotinamide), have been synthesized by the pre-assembly method and characterized by X-ray crystallography. In 1, CuII cations are bridged by meso-dpb ligands to form a one-dimensional (1D) linear chain. Compound 2 consists of 2D undulated layers of (4, 4) topology that show twofold parallel interpenetration. In the case of 3, the MI center adopts tetrahedral coordination geometry and the 2D networks are formed by organic ligand with “folding ruler-shaped” NCS-M chains. The thermal properties of 1-3 were also investigated.  相似文献   

15.
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   

16.
A metathesis reaction of [CpMCl2(PR3)] [M = Rh, R = Ph (1), Me (3); M = Ir, R = Ph (2), Me (4)] takes place in the presence of potassium butadienesulfinate (SO2CHCHCHCH2)K (9) to afford the mononuclear compounds [CpM(Cl)(PR3)(η1-SO2CHCHCHCH2)] [M = Rh, R = Ph (11S), (11W); M = Rh, R = Me (13S), (13W)] and [M = Ir, R = Ph (12S); M = Ir, R = Me (14S), (14W)] under different reaction conditions. The addition of PR3 (R = Ph, Me) to CpIr(Cl)[(1,2,5-η)-SO2CHCHCHCH2] (7) affords the corresponding iridium isomers 12S, 12W and 14S, in a non-selective reaction, along with the corresponding dichloride compounds 2 or 4. The 1H and 13C{1H} NMR data are consistent with the butadienesulfonyl ligands coordinated exclusively through the sulfur atom, and they show the presence of two isomers, described as the S and W conformers, which can be isolated separately. There is clear evidence that these isomers correspond to the kinetic and thermodynamic derivatives, respectively.  相似文献   

17.
Six lanthanide two-dimensional network coordination polymers with the general formula of [Ln(pmida)(NO3)(H2O)]n, where Ln = La (1), Nd (2), Sm (3), Gd (4), Dy (5), Er (6) and pmida2− = N-(2-pyridylmethyl)iminodiacetate, have been synthesized by hydrothermal process and characterized by elemental analysis, Infrared spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. All crystals are isostructural and crystallize in the monoclinic space group P21/a. The lanthanide(III) ion is nine-coordinated in a geometry of distorted tricapped trigonal prism by two N atoms and two O atoms from one pmida2− ligand, two bridging carboxylate O atoms from other two pmida2− ligands, two O atoms of a bidentate chelating nitrate and a O atom of a coordinated water molecule. The luminescent properties of [Sm(pmida)(NO3)(H2O)]n (3) and [Dy(pmida)(NO3)(H2O)]n (5) were investigated.  相似文献   

18.
Four copper(I) complexes of 2,11-dithia[3.3]paracyclophane (dtpcp), [CuI(dtpcp)] · MeCN (1), [CuBr(dtpcp)] · MeCN (2), [CuCl(dtpcp)] · MeCN (3) and [Cu2I2(dtpcp)2] · Me-thf (4) (Me-thf=2-methyltetrahydrofuran), have been synthesized and their molecular structures determined by X-ray crystallography. Complexes 1 and 2 are isostructural, and exhibit 3D networks with elliptical channels along a-axis, which are constructed by dtpcp molecules bridging zigzag CuI and CuBr chains, respectively. Complexes 3 and 4 are 2D porous sheet networks constructed by bridging the zigzag copper-dtpcp chains via rhombic ring of Cu2X2 (X=Cl or I). All sheets in 3 are packed in an eclipsed manner through π-π stackings to generate channels along the a-axis. However, the 2D porous sheets in 4 are packed in an offset mode such that channels are not formed along c-axis. Complexes 1 and 2 can reversibly incorporate guest acetonitriles without collapse of structures, and the original frameworks of 1 and 2 are completely recovered after incorporation of guests which are confirmed by X-ray powder diffraction (XRPD) pattern and 1H NMR spectrum. Additionally, complex 1 exhibits selectivity in size and polarity for guest inclusion.  相似文献   

19.
New CuII and NiII complexes of potentially tridentate N2O Schiff base ligands 1 and 2 have been synthesised and characterised. [Cu(2)(OH2)]+ possesses a square planar geometry in the solid state whereas [Ni(1)2] possesses a distorted octahedral geometry in which the amine donors of 1 coordinate weakly to the NiII centre. EPR spectroscopy demonstrates that the N2O2 coordination sphere of [Cu(2)(OH2)]+ is retained in CH2Cl2 solution. [Cu(2)(OH2)]+ exhibits a reversible one electron oxidation at E1/2 = 0.54 V versus [Fc]+/[Fc], the product of which has been characterised by UV-Vis absorption and EPR spectroscopies. The spectroscopic signature of the oxidised product is consistent with the formation of a stable phenoxyl radical ligand bound to a CuII centre. [Ni(1)2] possesses a reversible metal-based oxidation process at E1/2 = 0.03 V versus [Fc]+/[Fc] and a further oxidation, attributed to the generation of a phenoxyl radical centre, at  = 0.44 V versus [Fc]+/[Fc]. UV-Vis absorption and EPR spectroscopic studies indicate that the lower potential process is a formal NiIII/II couple. In contrast, the pro-ligands 1H and 2H exhibit chemically irreversible oxidation processes at  = 0.42 and 0.40 V versus Fc+/Fc, respectively, and do not support the formation of stable phenoxyl radical species.  相似文献   

20.
Three new polymeric mercury(II) thiocyanate coordination polymers, {[Hg2(L4)(SCN)4]n (1), [Hg2(μ-L5)(μ-SCN)4]n[Hg2(μ-L5)(μ-SCN)4]2n (2) and [Hg(L6)(SCN)2]n (3); L4 = 2,5-bis(2-pyridyl)-3,4-diaza-2,4-hexadiene, L5 = 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene and L6 = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene) were prepared from reactions of mercury(II) thiocyanate with three organic nitrogen donor-based ligands under thermal gradient conditions using the branched tube method and fully characterized by infrared spectroscopy, elemental analysis, thermo gravimetric analysis, and single crystal X-ray diffraction. The compounds are structurally diverse and show very interesting structural motifs: the compound 1 is one-dimensional heterochiral double-chains. In compound 2, the bridging ligand L5 adopts a transoid conformation and the network contains two interpenetrating coordination polymers, a 2D net and a 1D double-chain. The crystal structure of 3 consists of one-dimensional zigzag chains. Solid-state luminescent spectra of the compounds 1 and 3 indicate intense fluorescent emissions at ca. 393 nm and 363 nm, respectively.  相似文献   

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