共查询到20条相似文献,搜索用时 46 毫秒
1.
The crystalline compound [K([18]crown-6){C6H4(SiMe3)2-1,4}] (1) was prepared by the low-temperature reduction of the para-disilylated benzene with K/[18]crown-6 in toluene followed by recrystallisation from the same solvent. Reduction of 1,2,4,5-tetrasilylated benzene with 2(K/[18]crown-6) in toluene produced a hydrocarbon-insoluble powder identified as the dianionic derivative [K([18]crown-6)]2[C6H2(SiMe3)4-1,2,4,5)] (2), which upon crystallisation from THF/Et2O yielded [K([18]crown-6)(THF)2][C6H2(SiMe3)4-1,2,4,5] (3). An X-ray diffraction study revealed that 1 comprised a contact ion pair with the crown-encapsulated K cation η5-connected to the planar ring of the substituted benzene radical anion, while 3 contained a well separated cation and anion. 相似文献
2.
Wanda Ziemkowska Anna Kubiak Szymon Kucharski Robert Woźniak Romana Anulewicz-Ostrowska 《Polyhedron》2007
Reactions of Me5Al3[OC(C6H5)2C(C6H5)2O]2 (1) with alcohols ROH (R = Me, Et, tBu) in a 1:1 molar ratio afforded the compound Me2Al2[OC(C6H5)2C(C6H5)2O]2(C4H8O) (2) and a mixture of methylaluminum alkoxides. The alcohols acted as the factor formally eliminating a molecule of Me3Al (as a methylaluminum alkoxide) from compound 1. tBu3Al reacted with an equimolar amount of benzopinacol to form the monomeric complex tBuAl[OC(C6H5)2C(C6H5)2O](C4H8O) (3). Reactions of Me3Ga and Me3In with benzopinacol yielded trinuclear complexes Me5M3[OC(C6H5)2C(C6H5)2O]2 (4 (M = Ga), 5 (M = In)), isostructural to compound 1. In the presence of water and alcohols, compounds 4 and 5 underwent a decomposition reaction to benzopinacol and a mixture of metalloxanes and alkoxides. An unusual methylmethoxo indium benzopinacolate Me6In4[OC(C6H5)2C(C6H5)2O]2(OCH3)2 (6) was obtained in the reaction of benzopinacol with Me3In and Me2InOMe in a 1:1:1 molar ratio. Molecular structures of the compounds 3, 4 and 6 were determined by X-ray crystallography. 相似文献
3.
Yann Sarazin 《Journal of organometallic chemistry》2006,691(26):5680-5687
The new heteroleptic mercury(II) complex PhHgN(SiMe3)2(1) reacts with the strong Brønsted acid [H(OEt2)2][H2N{B(C6F5)3}2] with cleavage of a N-Si bond to give [C6H5Hg(H2NSiMe3)][H2N{B(C6F5)3}2] (2), a phenyl-mercury(II) cation stabilised by a primary amine and a non-coordinating counter-anion. Attempts to generate donor-free aryl mercury cations were not successful. The crystal structure of 2 · CH2Cl2 shows short π-bonding interactions between the metal and the phenyl ring of a neighbouring cation; the geometry about the mercury(II) atom is nearly linear. The X-ray structures of the new salts [H2N(SiMe3)2 · H3NSiMe3][B(C6F5)4]2 and [Et3O][H2N{B(C6F5)3}2] · CH2Cl2 are also presented. 相似文献
4.
The triosmium cluster 1,2-Os3(CO)10(MeCN)2 reacts rapidly with the diphosphine ligand 2,3-bis(diphenylphosphino)-N-p-tolylmaleimide (bmi) at room temperature to give bmi-bridged cluster 1,2-Os3(CO)10(bmi) (2b) as the major product, along with the chelating isomer 1,1-Os3(CO)10(bmi) (2c) and the hydride-bridged cluster HOs3(CO)9[μ-(PPh2)CC{PPh(C6H4)}C(O)N(tolyl-p)C(O)] (3) as minor by-products. All three cluster compounds have been isolated and fully characterized in solution by IR and NMR spectroscopies (1H and 31P), and X-ray crystallography in the case of 2c. Cluster 2b is unstable and readily isomerizes to 2c in quantitative yield on mild heating. The kinetics for the conversion of 2b → 2c have been measured over the temperature range of 318-348 K in toluene solution, and based on the observed activation parameters a nondissociative isomerization process that proceeds via a transient μ2-bridged phosphine moiety is presented. Near-UV photolysis of cluster 2c at room temperature affords HOs3(CO)9[μ-(PPh2)CC{PPh(C6H4)}C(O)N(tolyl-p)C(O)] (3) with a quantum yield of 0.017. The reactivity of clusters 2b, 2c, and 3 is discussed with respect to related diphosphine-substituted Os3(CO)10(P-P) clusters prepared by our groups. 相似文献
5.
Grant D.W. Anderson Malcolm L.H. Green Ino C. Vei 《Journal of organometallic chemistry》2004,689(24):4407-4419
Reactions between [Fe(η-C5H5)(MeCO)(CO)(L)], L = PPh3 (1), PMe3 (2), PPhMe2 (3), PCy3 (4), CO (5), and B(C6F5)3 give new complexes [Fe(η-C5H5){MeCOB(C6F5)3}(CO)(L)] L = PPh3 (7), PMe3 (8), PPhMe2 (9), PCy3 (10), CO (11), where B(C6F5)3 coordinates selectively to the O-acyl groups. Hydrolysis of 7 gives [Fe(η-C5H5){HOB(C6F5)3}(CO)(PPh3)] (6). The X-ray structures of 6, 8 and 11 have been determined. Calculations, using density functional theory, demonstrate that the charge transfer to the acyl group on Lewis acid coordination is more significant in the σ than the π system. Both effects lead to a lengthening of the acyl C-O bond thus π populations cannot be inferred from the distance changes. 相似文献
6.
Sergey A. Belov Dmitrii P. Krut’ko Dmitrii A. Lemenovskii Judith A.K. Howard 《Journal of organometallic chemistry》2008,693(10):1912-1918
Novel half-sandwich [C9H5(SiMe3)2]ZrCl3 (3) and sandwich [C9H5(SiMe3)2](C5Me4R)ZrCl2 (R = CH3 (1), CH2CH2NMe2 (2)) complexes were prepared and characterized. The reduction of 2 by Mg in THF lead to (η5-C9H5(SiMe3)2)[η5:η2(C,N)-C5Me4CH2CH2N(Me)CH2]ZrH (7). The structure of 7 was proved by NMR spectroscopy data. Hydrolysis of 2 resulted in the binuclear complex ([C5Me4CH2CH2NMe2]ZrCl2)2O (6). The crystal structures of 1 and 6 were established by X-ray diffraction analysis. 相似文献
7.
The reaction between BaI2 · 2H2O and NaHFIP [HFIP = OCH(CF3)2] in a 1:1 stoichiometry gave the heterometallic compound NaBaI2(HFIP)(H2O)(THF)0.5 (1). Attempts to recrystallize 1 in the presence of N- or O-donor ligands lead to redistribution reactions. Barium iodide adducts such as BaI2(DME)3 (2), trans-BaI2(DME)(triglyme) (3) and cis-BaI2(DME)(tetraglyme) (4) were isolated with DME as solvent. A similar behavior was observed for the reaction between BaI2 · 2H2O and NaTFA (TFA = O2CCF3) in a 1:1 stoichiometry in THF, and [Ba(tetraglyme)2]I2 · C7H8 (6) was isolated in the presence of excess tetraglyme. All compounds have been characterized by elemental analysis, IR and 1H NMR as well as single crystal X-ray studies for 3, 4 and 6. Compounds 3 and 4 are covalent adducts with eight- and nine-coordinate barium, respectively. Compound 6 is an ionic compound where two tetraglyme ligands wrap the 10-coordinate barium cation in a helical fashion. The presence of DME actually allows the coordination number of barium in the mixed-ligand adducts 3 and 4 to be tuned. The average Ba–O bond lengths (2.80 for 3 to 2.87 Å for 6) reflect the coordination number of the metal. The same observation is valid for the average Ba–I bond distance, 3.442 for 3 vs. 3.536 Å for 4. 相似文献
8.
Rubén A. Machado María Cristina Goite Ysaura De Sanctis Antony J. Deeming Anibal Sierralta Teresa González 《Journal of organometallic chemistry》2007,692(4):894-902
The reaction of the labile compound [Re2(CO)8(CH3CN)2] with 2,3-bis(2-pyridyl)pyrazine in dichloromethane solution at reflux temperature afforded the structural dirhenium isomers [Re2(CO)8(C14H10N4)] (1 and 2), and the complex [Re2(CO)8(C14H10N4)Re2(CO)8] (3). In 1, the ligand is σ,σ′-N,N′-coordinated to a Re(CO)3 fragment through pyridine and pyrazine to form a five-membered chelate ring. A seven-membered ring is obtained for isomer 2 by N-coordination of the 2-pyridyl groups while the pyrazine ring remains uncoordinated. For 2, isomers 2a and 2b are found in a dynamic equilibrium ratio [2a]/[2b] = 7 in solution, detected by 1H NMR (−50 °C, CD3COCD3), coalescence being observed above room temperature. The ligand in 3 behaves as an 8e-donor bridge bonding two Re(CO)3 fragments through two (σ,σ′-N,N′) interactions. When the reaction was carried out in refluxing tetrahydrofuran, complex [Re2(CO)6(C14H10N4)2] (4) was obtained in addition to compounds 1-3. The dinuclear rhenium derivative 4 contains two units of the organic ligand σ,σ′-N,N′-coordinated in a chelate form to each rhenium core. The X-ray crystal structures for 1 and 3 are reported. 相似文献
9.
Wen-Yann Yeh Yen-Chung Liu Gene-Hsiang Lee 《Journal of organometallic chemistry》2004,689(6):1014-1018
[Cp4Fe4(CO)4] (1) reacts with p-BrC6H4Li and MeOH in sequence to afford the functionalized cluster [Cp3Fe4(CO)4(C5H4-p-C6H4Br)] (2), while the reaction of 2 with n-BuLi and MeOH produces [Cp2Fe4(CO)4(C5H4Bu)(C5H4-p-C6H4Br)] (3). The double cluster [Cp3Fe4(CO)4(C5H4)]2(p-C6H4) (4) has been prepared by treatment of [Cp4Fe4(CO)4] with p-C6H4Li2 and MeOH in sequence. The electrochemistry of 2 and 4, as well as the crystal structure of 4 have been investigated. 相似文献
10.
This work reports on the preparation of the complexes [PdCl2(Y1)2], [PdCl2(Y2)2] (Y1 = (p-tolyl)3PCHCOCH3 (1a); Y2 = Ph3PCHCO2CH2Ph (1b)), [Pd{CHP(C7H6)(p-tolyl)2COCH3}(μ-Cl)]2 (2a), [Pd{CHP(C6H4)Ph2CO2CH2Ph}(μ-Cl)]2 (2b), [Pd{CH{P(C7H6)(p-tolyl)2}COCH3}Cl(L)] (L = PPh3 (3a), P(p-tolyl)3 (4a)) and [Pd{CH{P(C6H4)Ph2}CO2CH2Ph}Cl(L)] (L = PPh3 (3b), P(p-tolyl)3 (4b)). Orthometallation and ylide C-coordination in complexes 2a–4b are demonstrated by an X-ray diffraction study of 4a. 相似文献
11.
Reactions of [Pt2(μ-Cl)2(C8H12OMe)2] (1) (C8H12OMe = 8-methoxy-cyclooct-4-ene-1-yl) with various anionic chalcogenolate ligands have been investigated. The reaction of 1 with Pb(Spy)2 (HSpy = pyridine-2-thiol) yielded a binuclear complex [Pt2(Spy)2(C8H12OMe)2] (2). A trinuclear complex [Pt3(Spy)4(C8H12OMe)2] (3) was isolated by a reaction between 2 and [Pt(Spy)2]n. The reaction of 1 with HSpy in the presence of NaOMe generated 2 and its demethylated oxo-bridged tetranuclear complex [Pt4(Spy)4(C8H12-O-C8H12)2] (4). Treatment of 1 with ammonium diisopropyldithiophosphate completely replaced C8H12OMe resulting in [Pt(S2P{OPri}2)2] (5), whereas non-rigid 5-membered chelating ligand, Me2NCH2CH2E−, produced mononuclear complexes [Pt(ECH2CH2NMe2)(C8H12OMe)] (E = S (6), Se (7)). These complexes have been characterized by elemental analyses, NMR (1H, 13C{1H}, 195Pt{1H}) and absorption spectroscopy. Molecular structures of 2, 3, 4, 5 and 7 were established by single crystal X-ray diffraction analyses. Thermolysis of 2, 6 and 7 in HDA gave platinum nanoparticles. 相似文献
12.
The title compound (1) was prepared by the reaction of 3,5-bis(CF3)C6H3P(i-C3H7)2 (L1) and Co2(CO)8. Its solubility in supercritical carbon dioxide was measured at varying temperatures and pressures using a modified analytical extraction device. Solubility data were determined in the temperature and pressure ranges between 40 and 70 °C and between 100 and 300 bar, respectively. The solubility of 1 is lower compared to (p-CF3C6H4)3P, but much higher than for transition metal complexes bearing phosphines without fluorinated substituents. 相似文献
13.
Masato Ohashi 《Journal of organometallic chemistry》2006,691(11):2457-2464
Reaction of a triangle Pd(0) complex, Pd3(CNXyl)6 (1; Xyl = 2,6-C6H3Me2), with a dicationic linear trinuclear complex [Pd3(CNXyl)8][PF6]2 (3) afforded a dicationic hexapalladium complex [Pd6(CNXyl)12][PF6]2 (4), while the reaction of 1 with a dicationic dinuclear complex [Pd2(CNXyl)6][PF6]2 (2) resulted in the formation of 3. The molecular structure of the complex 4 was determined by X-ray crystallography and spectroscopic analysis. 相似文献
14.
Benito Flores-Chávez José G. Alvarado-Rodríguez Noemí Andrade-López Verónica García-Montalvo Eliazar Aquino-Torres 《Polyhedron》2009
Treatment of RnGeCl4−n with {S(C6H3SH)2O} (1) afforded the stable phenoxathiin-4,6-dithiolate compounds [{S(C6H3S)2O}GeR2] [n = 2; R = Et (2), Ph (3)] and [{S(C6H3S)2O}GeRCl] [n = 1; R = Et (4), Ph (5)]. Treatment of GeCl4 with 1 in benzene afforded the dichloro compound [{S(C6H3S)2O}GeCl2] (8) at 7 °C. Bromo compounds [{S(C6H3S)2O}GeRBr] [R = Et (6), Ph (7)] and [{S(C6H3S)2O}GeBr2] (9) were synthesized by halogen exchange from the appropriate chloro derivative using KBr/HBr. X-ray structure determinations of diorganyl dithiolate compounds 2 and 3 revealed that germanium atom is contained in a boat–chair-shaped eight-membered central ring and displays a tetrahedral geometry. In contrast, compounds 4–6 display a boat–boat-shaped central ring with a significant intramolecular transannular O···Ge interaction. The geometry of the pentacoordinate Ge atom in these last complexes may be described as distorted trigonal bipyramidal with a 62–65% distortion displacement. 相似文献
15.
Five organic-inorganic hybrid gallium oxalate-phosphates, [Ga2(PO4)2(H2O)(C2O4)0.5](C3N2H12)0.5(H2O) (1), [Ga2(PO4)2(C2O4)0.5](C2N2H10)0.5(H2O) (2), [Ga2(PO4)2(C2O4)0.5](C3N2H12)0.5 (3), [Ga2(PO4)2(H2PO4)0.5(C2O4)0.5](C4N3H16)0.5 (H2O)1.5 (4) and [Ga2.5(PO4)2.5(H2O)1.5(C2O4)0.5](C4N3H15)0.5 (5), have been synthesized by using 1,3-diaminopropane, ethylenediamine and diethylene triamine as structure-directing agents under hydrothermal condition. The structures of 1-5 are based on Ga4(PO4)4(C2O4) building unit made up from Ga2O8(C2O4) oxalate-bridging dimer and alternating PO4 and GaO4 tetrahedral units. Compound 1 is layered structure where the building units link together in the same orientation. Corner sharing of these similar layers result in three-dimensional (3-D) structure 2. However, in compound 3, the building units arrange in a wave-like way to generate two types of eight member ring (8MR) channels. Both 4 and 5 contain the layers where the building units have an opposite orientation. Those layers are linked by H2PO4 group and Ga(PO4)(H2O)3 cluster, respectively, to form 3-D frameworks with 12MR large pore channels. Compounds 2-5 exhibit intersecting 3-D channels where the protoned amines are located. 相似文献
16.
Swadhin K. Mandal Setharampattu S. Krishnamurthy Thomas Stey 《Journal of organometallic chemistry》2005,690(3):742-750
Chiral “P-N-P” ligands, (C20H12O2)PN(R)PY2 [R = CHMe2, Y = C6H5 (1), OC6H5 (2), OC6H4-4-Me (3), OC6H4-4-OMe (4) or OC6H4-4-tBu (5)] bearing the axially chiral 1,1′-binaphthyl-2,2′-dioxy moiety have been synthesised. Palladium allyl chemistry of two of these chiral ligands (1 and 2) has been investigated. The structures of isomeric η3-allyl palladium complexes, (R′ = Me or Ph; Y = C6H5 or OC6H5) have been elucidated by high field two-dimensional NMR spectroscopy. The solid state structure of [Pd(η3-1,3-Ph2-C3H3){κ2-(racemic)-(C20H12O2)PN(CHMe2)PPh2}](PF6) has been determined by X-ray crystallography. Preliminary investigations show that the diphosphazanes, 1 and 2 function as efficient auxiliary ligands for catalytic allylic alkylation but give rise to only moderate levels of enantiomeric excess. 相似文献
17.
Franc Perdih 《Journal of fluorine chemistry》2006,127(10):1289-1293
[Na{Ti2(C5Me5)2F7}] (1) was prepared from sodium fluoride and [{Ti(C5Me5)F3}2] [H.W. Roesky, et al., Angew. Chem. Int. Ed. Engl. 31 (1992) 864-866]. The solid-state 1 consists of a polymeric chain of two rows of dititanate anions [Ti2(C5Me5)2F7]− connected by sodium ions in the middle of the chain. Each sodium ion is coordinated by five fluorine atoms from three [Ti2(C5Me5)2F7]− anions. The variable-temperature 19F NMR of CD3CN solution of 1 revealed interconversions of monomeric species [Na(CD3CN)n{Ti2(C5Me5)2F7}] (1solv) with different number of CD3CN ligands on the sodium ion. The addition of HMPA to the CD3CN solution of 1 allows 19F NMR observation of 1·HMPA (1a) and 1·HMPA·CD3CN (1b) in the slow exchange. The solid-state structure of [NaTi6(C5Me5)5F20(H2O)]·(THF) (2·THF) reveals the sodium ion coordinated by four fluorine atoms from the anion [Ti2(C5Me5)2F7]− and by three fluorine atoms from the cluster [Ti4(C5Me5)3F13(H2O)]. 相似文献
18.
Monika Kulcsar Cristian Silvestru John E. Drake Michael E. Hursthouse 《Journal of organometallic chemistry》2005,690(13):3217-3228
The cleavage of the Se-Se bond in [2-(Me2NCH2)C6H4]2Se2 (1) was achieved by treatment with SO2Cl2 (1:1 molar ratio) or elemental halogens to yield [2-(Me2NCH2)C6H4]SeX [X = Cl (2), Br (3), I (4)]. Oxidation of 1 with SO2Cl2 (1:3 molar ratio) gave [2-(Me2NCH2)C6H4]SeCl3 (5). [2-(Me2NCH2)C6H4]SeS(S)CNR2 [R = Me (6), Et (7)] were prepared by reacting [2-(Me2NCH2)C6H4]SeBr with Na[S2CNR2] · nH2O (R = Me, n = 2; R = Et, n = 3). The reaction of 3 with K[(SPMe2)(SPPh2)N] resulted in isolation of [2-(Me2NCH2)C6H4]Se-S-PMe2N-PPh2S (8). The compounds were characterized by solution NMR spectroscopy (1H, 13C, 31P, 77Se, 2D experiments). The solid-state molecular structures of 2, 4-8 were established by single crystal X-ray diffraction. All compounds are monomeric, with the N atom of the pendant CH2NMe2 arm involved in a three-center-four-electron N?Se-X (X = halogen, S) bond. This results in a T-shaped coordination geometry for the Se(II) atom in 2, 4, 6-8. In 5, the Se(IV) atom achieves a square pyramidal coordination in the mononuclear unit. Loosely connected dimers are formed through intermolecular Se?Cl interactions (3.40 Å); the overall coordination geometry being distorted octahedral. In all compounds hydrogen bonds involving halide or sulfur atoms generate supramolecular associations in crystals. 相似文献
19.
Maria S. Tarasenko Nikolay G. Naumov Dmitry Yu. Naumov Sung-Jin Kim Vladimir E. Fedorov 《Polyhedron》2008
A series of new compounds containing rare earth cations (Eu to Yb) and paramagnetic cluster anion [Re6Te8(CN)6]3− was prepared and investigated. The X-ray structural analyses have revealed that the compounds [{Ln(H2O)4}{Re6Te8(CN)6}] · 2.5H2O; Ln = Eu (1), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), [{Gd(H2O)3}{Re6Te8(CN)6}] · 2.5H2O (2) and [{Yb(H2O)4}{Re6Te8(CN)6}] (8) are three-dimensional polymers based on Re–CN–Ln interactions. Measurements of magnetic susceptibility for 2 and 5 showed that effective magnetic moment (at 300 K) was 8.13 μB for compound 2 and 10.79 μB for compound 5 with weak antiferromagnetic ordering appeared at low temperatures. 相似文献
20.
Yang Yang 《Journal of solid state chemistry》2011,184(7):1666-1670
A new organically templated pentaborate [C6N4H20]0.5[B5O6(OH)4] (1a) was prepared by reactions of triethylenetetramine (TETA) with excess boric acid in aqueous solution and characterized by elemental analysis, FTIR, TG-DTA, powder X-ray diffraction and photoluminescence spectroscopy. The structure of 1a was determined by a single-crystal X-ray diffraction. It crystallizes in the monoclinic system with space group P2(1)/c, a=9200(3) Å, b=14.121(5) Å, c=10.330(4) Å, β=91.512(4)°, V=1341.4(9) Å3, and Z=4. The luminescent properties of the compound were studied, and a green-blue luminescence occurs with an emission maximum at 507 nm upon excitation at 430 nm. The photoluminescence of 1a can be modified from green-blue to white by means of a simple heat-treatment process. The white-light-emission of sample 1c makes the pentaborate a good candidate for display and lighting applications in the white LED. 相似文献