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1.
The salts [S(NMe2)3][MF6] (M = Nb, 2a; M = Ta, 2b) and [S(NMe2)3][M2F11] (M = Nb, 2c; M = Ta, 2d) have been prepared by reacting MF5 (M = Nb, 1a; M = Ta, 1b) with [S(NMe2)3][SiMe3F2] (TASF reagent) in the appropriate molar ratio. The solid state structure of 2b has been ascertained by X-ray diffraction. The 1:1 molar ratio reactions of 1a with a variety of organic compounds (L) give the neutral adducts NbF5L [L = Me2CO, 3a; L = MeCHO, 3b; L = Ph2CO, 3c; L = tetrahydrofuran (thf), 3d; L = MeOH, 3e; L = EtOH, 3f; L = HOCH2CH2OMe, 3g; L = Ph3PO, 3h; L = NCMe, 3i] in good yields. The complexes MF5L [M = Nb, L = HCONMe2, 3j; M = Nb, L = (NMe2)2CO, 3k; M = Ta, L = (NMe2)2CO, 3l; M = Nb, L = OC(Me)CHCMe2, 3m] have been detected in solution in admixture with other unidentified products, upon 2:1 molar reaction of 1 with the appropriate reagent L. The ionic complexes [NbF4(tht)2][NbF6], 4a, and [NbF4(tht)2][Nb2F11], 4b, have been obtained by combination of tetrahydrothiophene (tht) and 1a, in 1:1 and 2:3 molar ratios, respectively. The treatment of 1 with a two-fold excess of L leads to the species [MF4L4][MF6] [M = Nb, L = HCONMe2, 5a; M = Ta, L = HCONMe2, 5b; M = Nb, L = thf, 5c; M = Ta, L = thf, 5d; M = Nb, L = OEt2, 5e]. The new complexes have been fully characterised by NMR spectroscopy. Moreover, the revised 19F NMR features of the known compounds MF5L [M = Ta, L = Me2CO, 3n; M = Ta, L = Ph2CO, 3o; M = Ta, L = MePhCO, 3p; M = Ta, L = thf, 3q; M = Nb, L = CH3CO2H, 3r; M = Nb, L = CH2ClCO2H, 3s; M = Ta, L = CH2ClCO2H, 3t], TaF4(acac), TaF4(Me-acac) and [TaF(Me-acac)3][TaF6] (Me-acac = methylacetylacetonato anion) are reported. 相似文献
2.
The reaction of cis-[RuCl2(DMSO)4] with a family of aromatic and heterocyclic acid hydrazides yielded new complexes of the general formula trans-[RuCl2(DMSO)2(hydrazide)] · nH2O (n = 0; 1–6; n = 1; 7). The new complexes have been characterized by IR, UV–Vis and 1H NMR spectroscopic methods. In addition, the structure of one of the complexes, [RuCl2(DMSO)2(tcah)] · H2O (tcah = thiophene-2-carboxylic acid hydrazide), has been determined by single crystal X-ray diffraction. All the studies reveal the neutral bidentate coordination of the hydrazide ligands through the acyl oxygen and amine nitrogen atoms. The electron transfer properties of the complexes were studied by cyclic voltammetry and all the complexes except one show an irreversible/quasi-reversible reduction wave (RuII/RuI) and an uncoupled oxidation peak (RuIII/ RuII). The preliminary DNA-binding ability of the complexes, studied with herring sperm DNA, shows the binding of the complexes with DNA with a lesser affinity than classical intercalators. The complexes have also been screened for their antibacterial activity against five pathogenic bacteria. 相似文献
3.
Four metal complexes based on the phenyl-bridged pyridine ligand with tetrathiafulvalene unit (TTF-Ph-Py, L), NiII(acac)2(L)2 (1, acac = acetylacetonate), M(hfac)2(L)2 (M = NiII, 2; M = CuII, 3; hfac = hexafluoroacetylacetonato) and [CoII(TpPh2)(OAc)(L)]·H2O (4, TpPh2 = hydridotri(3,5-diphenylpyrazol-1-yl) borate), have been synthesized and structurally characterized. The absorption spectra and redox behaviors of these new compounds have been studied. Optimized conformation and molecular orbital diagram of L has been calculated with density functional theory (DFT). 相似文献
4.
Konstantina A. Kounavi Constantina Papatriantafyllopoulou Anastasios J. Tasiopoulos Spyros P. Perlepes Vassilios Nastopoulos 《Polyhedron》2009
An investigation of the MII/X−/L [MII = Co, Ni, Cu, Zn; X− = Cl−, Br−, I−, NCS−, NO3−, N3−, CH3COO−; L = 1-methyl-4,5-diphenylimidazole] general reaction system towards the detailed study of the intermolecular interactions utilized for controlling the supramolecular organization and the structural consequences on the structures produced has been initiated. Three representative complexes with the formulae [Co(NO3)2(L)2] (1), [Zn(NO3)2(L)2] (2) and [Co(NCS)2(L)2]·EtOH (3·EtOH) have been synthesized and characterized by spectroscopic methods and single-crystal X-ray analysis. Compounds 1 and 2 are isomorphous (tetragonal, I41cd) with their metal ions in a severely distorted octahedral Co/ZnN2O4 environment, while 3·EtOH crystallizes in P21/c with a tetrahedral CoN4 coordination. The structural analysis of 1, 2 and 3·EtOH reveals a common mode of packing among neighbouring ligands (expressed through intramolecular π–π interactions between the 4,5-diphenylimidazole moieties), enhancing thus the rigidity and stability of the complexes. The bent coordination of the two isothiocyanates in 3 [Co–NCS angles of 173.8(2) and 160.8(2)°] seems to be caused by intermolecular hydrogen bonding and crystal packing effects. 相似文献
5.
Ching-Shiang Fang 《Journal of organometallic chemistry》2009,694(3):404-1617
Mononuclear complexes of the type, M(CO)4[Se2P(OR)2] (M = Mn, R = iPr, 1a; Et, 1b; M = Re, R = iPr, 3a; Et, 3b) can be prepared from either [-Se(Se)P(OiPr)2]2 (A) or [Se{-Se(Se)P(OEt)2}2] (B) with M(CO)5Br. O,O′-dialkyl diselenophosphate ([(RO)2PSe2]-, abbreviated as dsep) ligands generated from A and B act as a chelating ligand in these complexes. Upon refluxing in acetonitrile, these mononuclear complexes yield dinuclear complexes with a general formula of [M2(CO)6{Se2P(OR)2}2] (M = Mn, R = iPr, 2a; Et, 2b; M = Re, R = iPr, 4a; Et, 4b). Dsep ligands display a triconnective, bimetallic bonding mode in the dinuclear compounds and this kind of connective pattern has never been identified in any phosphor-1,1-diselenoato metal complexes. Compounds 2b, 3b, and 4 are structurally characterized. Compounds 2b and 3b display weak, secondary Se?Se interactions in their lattices. 相似文献
6.
Mononuclear complexes of cyclodiphosphazane with an uncoordinated phosphorus centre [RuCl2(η6-cymene){l-κP}] (1a) (L = cis-{(o-MeOC6H4O)P(μ-NtBu)}2) and [PdCl2(PEt3){l-κP}] (1b) react with 1 equiv. of [AuCl(SMe2)] to afford RuII/AuI and PdII/AuI heterodinuclear complexes [RuCl2(η6-cymene){μ-l-κP,κP}AuCl] (2) and [PdCl2(PEt3){μ-l-κP,κP}AuCl] (3), respectively. Heterotrinuclear complexes [PdCl2{μ-l-κP,κP}2(AuCl)2] (4), [PtCl2{μ-l-κP,κP}2(AuCl)2] (5) and [CuI{μ-l-κP,κP}2(AuCl)2] (6) containing PdII/2AuI, PtII/2AuI and CuI/2AuI metal centers have been synthesized from the reactions of trans-[PdCl2{l-κP}2] (1c), cis-[PtCl2{l-κP}2] (1d) and [CuI{{l-κP}2] (1f) respectively, with 2 equiv. of [AuCl(SMe2)]. Molecular structures of complexes 2, 3 and 4 were established by single crystal X-ray diffraction studies. 相似文献
7.
Piotr Jaunky 《Journal of organometallic chemistry》2005,690(6):1429-1455
An efficient route to the novel tridentate phosphine ligands RP[CH2CH2CH2P(OR′)2]2 (I: R = Ph; R′ = i-Pr; II: R = Cy; R′ = i-Pr; III: R = Ph; R′ = Me and IV: R = Cy; R′ = Me) has been developed. The corresponding ruthenium and iron dicarbonyl complexes M(triphos)(CO)2 (1: M = Ru; triphos = I; 2: M = Ru; triphos = II; 3: M = Ru; triphos = III; 4: M = Ru; triphos = IV; 5: M = Fe; triphos = I; 6: M = Fe; triphos = II; 7: M = Fe; triphos = III and 8: M = Fe; triphos = IV) have been prepared and fully characterized. The structures of 1, 3 and 5 have been established by X-ray diffraction studies. The oxidative addition of MeI to 1-8 produces a mixture of the corresponding isomeric octahedral cationic complexes mer,trans-(13a-20a) and mer,cis-[M(Me)(triphos)(CO)2]I (13b-20b) (M = Ru, Fe; triphos = I-IV). The structures of 13a and 20a (as the tetraphenylborate salt (21)) have been verified by X-ray diffraction studies. The oxidative addition of other alkyl iodides (EtI, i-PrI and n-PrI) to 1-8 did not afford the corresponding alkyl metal complexes and rather the cationic octahedral iodo complexes mer,cis-[M(I)(triphos)(CO)2]I (22-29) (M = Ru, Fe; triphos = I-IV) were produced. Complexes 22-29 could also be obtained by the addition of a stoichiometric amount of I2 to 1-8. The structure of 22 has been verified by an X-ray diffraction study. Reaction of 13a/b-20a/b with CO afforded the acetyl complexes mer,trans-[M(COMe)(triphos)(CO)2]I, 30-37, respectively (M = Ru, Fe; triphos = I-IV). The ruthenium acetyl complexes 30-33 reacted slowly with 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) even in boiling acetonitrile. Under the same conditions, the deprotonation reactions of the iron acetyl complexes 34-37 were completed within 24-40 h to afford the corresponding zero valent complexes 5-8. It was not possible to observe the intermediate ketene complexes. Tracing of the released ketene was attempted by deprotonation studies on the labelled species mer,trans-[Fe(COCD3)(triphos)(CO)2]I (38) and mer,trans-[Fe(13COMe)(triphos)(CO)2]I (39). 相似文献
8.
Andrea Albertino Simona Ghiani Carlo Nervi Edward Rosenberg Guido Viscardi Gianluca Croce 《Journal of organometallic chemistry》2007,692(6):1377-1391
We report a combined experimental and computational study of new rhenium tricarbonyl complexes based on the bidentate heterocyclic N-N ligands 2-(4-methylpyridin-2-yl)benzo[d]-X-azole (X = N-CH3, O, or S) and 2-(benzo[d]-X-azol-2-yl)-4-methylquinoline (X = N-CH3, O, or S). Two sets of complexes are reported. Chloro complexes, described by the general formula Re(CO)3[2-(4-methylpyridin-2-yl)benzo[d]-X-azole]Cl (X = N-CH3, 1; X = O, 2; X = S, 3) and Re(CO)3[2-(benzo[d]-X-azol-2-yl)-4-methylquinoline]Cl (X = N-CH3, 4; X = O, 5; X = S, 6) were synthesized heating at reflux Re(CO)5Cl with the appropriate N-N ligand in toluene. The corresponding pyridine set {Re(CO)3[2-(4-methylpyridin-2-yl)benzo-X-azole]py}PF6 (X = N-CH3, 7; X = O, 8; X = S, 9) and {Re(CO)3[2-(benzo[d]-X-azol-2-yl)-4-methylquinoline]py}PF6 (X = N-CH3, 10; X = O, 11; X = S, 12) was synthesized by halide abstraction with silver nitrate of 1-6 followed by heating in pyridine and isolated as their hexafluorophosphate salts. All complexes have been fully characterized by IR, NMR, electrochemical techniques and luminescence. The crystal structures of 1 and 7 were obtained by X-ray diffraction. DFT and time-dependent (TD) DFT calculations were carried out for investigating the effect of the organic ligand on the optical properties and electronic structure of the reported complexes. 相似文献
9.
Kerwyn G. Alley Roland Bircher Hans U. Güdel Boujemaa Moubaraki Keith S. Murray Brendan F. Abrahams Colette Boskovic 《Polyhedron》2007
The reaction of Ni(OAc)2, NiX2 (X = Cl, Br) or CoCl2 with the proligand 2-amino-2-methyl-1,3-propanediol (ampdH2) affords a new family of tetranuclear complexes. The syntheses of [Ni4(OAc)4(ampdH)4] (1) and [M4X4(ampdH)4] (M = Ni, X = Cl, 2; M = Ni, X = Br, 3; M = Co, X = Cl, 4) are reported, together with the single crystal X-ray structures of 1, 2 and 4 and the magnetochemical characterization of 1, 3 and 4. Each member of this family of complexes displays a low symmetry structure that incorporates a {M4O4} core unit based on a distorted cubane. Magnetic measurements reveal ferromagnetic exchange interactions for 1, 3 and 4. These give rise to S = 4 ground state spins for the tetranuclear Ni complexes and an anisotropic effective S′ = 2 ground state for the Co complex. 相似文献
10.
Gustavo Von Poelhsitz André L. Bogado Luciano M. Lião Antonio G. Ferreira Eduardo E. Castellano Javier Ellena Alzir A. Batista 《Polyhedron》2010
This study presents the syntheses and characterization of 2-mercaptopyridine (pyS−) complexes containing ruthenium(II) with the following general formula [Ru(pyS)2(P–P)], P–P = (c-dppen) = cis-1,2-bis(diphenylphosphino)ethylene) (1); (dppe) = 1,2-bis(diphenylphosphino)ethane (2); (dppp) = 1,3-bis(diphenylphosphino)propane (3) and (dppb) = 1,4-bis(diphenylphosphino)butane (4). The complexes were synthesized from the mer- or fac-[RuCl3(NO)(P–P)] precursors in the presence of triethylamine in methanol solution with dependence of the product on the P–P ligand. The reaction of pyS− with a ruthenium complex containing a bulky aromatic diphosphine dppb disclosed a major product with a dangling coordinated dppbO-P, the [Ru(pyS)2(NO)(η1-dppbO-P)]PF6(5). In addition, this work also presents and discusses the spectroscopic and electrochemical behavior of 1–5, and report the X-ray structures for 1 and 5. 相似文献
11.
A series of new triorganotin(IV) pyridinecarboxylates with 6-hydroxynicotinic acid (6-OH-3-nicH), 5-hydroxynicotinic acid (5-OH-3-nicH) and 2-hydroxyisonicotinic acid (2-OH-4-isonicH) of the types: [R3Sn (6-OH-3-nic)·L]n (I) (R = Ph, L = Ph·EtOH, 1; R = Bn, L = H2O·EtOH, 2; R = Me, L = 0, 3; R = n-Bu, L = 0, 4), [R3Sn (5-OH-3-nic)]n (II) (R = Ph, 5; R = Bn, 6; R = Me, 7; R = n-Bu, 8), [R3Sn (2-OH-4-isonic·L)]n (III) (R = Bn, 9, L = MeOH; R = Me, L = 0, 10; R = Ph, 11, L = 0.5EtOH) have been synthesized. All the complexes were characterized by elemental analysis, TGA, IR and NMR (1H, 13C, 119Sn) spectroscopy analyses. Among them, except for complexes 5 and 6, all complexes were also characterized by X-ray crystallography diffraction analysis. Crystal structures show that complexes 1-10 adopt 1D infinite chain structures which are generated by the bidentate O, O or N, O and the five-coordinated tin centers. Significant O-H?O, and N-H?O intermolecular hydrogen bonds stabilize these structures. Complex 11 is a 42-membered macrocycle containing six tin atoms, and forms a 2D network by intermolecular N-H?O hydrogen. 相似文献
12.
Niobium and tantalum pentahalides, MX5 (1), react with acetic acid and halo-substituted acetic acids, in 1:1 ratio, to give the dinuclear complexes [MX4(μ-OOCMe)]2 [M = Nb, X = Cl, 2a; M = Ta, X = Cl, 2b; Br, 2c] and [MCl4(μ-OOCR)]2 [M = Nb, R = CH2Cl, 4a; CHCl2, 4c; CCl3, 4e; CF3, 4g; CHBr2, 4i; CH2I, 4j; M = Ta, R = CH2Cl, 4b; CHCl2, 4d; CCl3, 4f; CF3, 4h]. The solid state structures of 2b and 4e have been ascertained by X-ray diffraction studies. The reactions of 1 with acetic anhydride and halo-substituted acetic anhydrides result in C–O bond activation and afford 2 and 4, respectively, with concomitant formation of acetyl halides. Moreover, the complexes MCl5[OC(Cl)Me] [M = Nb, 3a; M = Ta, 3b] have been detected in significant amounts within the mixtures of the reactions of MCl5 with acetic anhydride. TaI5 is unreactive, at room temperature, towards both MeCOOH and (MeCO)2O. MF5 react with RCOOH (R = Me, CH2Cl) in 1:1 molar ratio, to afford the ionic compounds [MF4(RCOOH)2][MF6], 5a–d, in high yields. The additions of (RCO)2O (R = Me, CH2Cl) to MF5 give 5, suggesting that anhydride C–H and C–O bonds activation is operative during the course of these reactions. 相似文献
13.
Animesh Patra Sandipan Sarkar Michael G.B. Drew Ennio Zangrando Pabitra Chattopadhyay 《Polyhedron》2009
Three new mononuclear complexes of nitrogen–sulfur donor sets, formulated as [FeII(L)Cl2] (1), [CoII(L)Cl2] (2) and [NiII(L)Cl2] (3) where L = 1,3-bis(2-pyridylmethylthio)propane, were synthesized and isolated in their pure form. All the complexes were characterized by physicochemical and spectroscopic methods. The solid state structures of complexes 1 and 3 have been established by single crystal X-ray crystallography. The structural analysis evidences isomorphous crystals with the metal ion in a distorted octahedral geometry that comprises NSSN ligand donors with trans located pyridine rings and chlorides in cis positions. In dimethylformamide solution, the complexes were found to exhibit FeII/FeIII, CoII/CoIII and NiII/NiIII quasi-reversible redox couples in cyclic voltammograms with E1/2 values (versus Ag/AgCl at 298 K) of +0.295, +0.795 and +0.745 V for 1, 2 and 3, respectively. 相似文献
14.
Luigi Busetto Mauro Salmi Valerio Zanotti 《Journal of organometallic chemistry》2007,692(11):2245-2252
The bridging diiron thiocarbyne complex [Fe2{μ-CS(Me)}(μ-CO)(CO)2(Cp)2][SO3CF3] (1) reacts with activated olefins (methyl acrylate, acrylonitrile, styrene, diethyl maleate), in the presence of Me3NO and NaH, to give the corresponding μ-allylidene complexes [Fe2{μ-η1:η3-Cα(SMe)Cβ(R′)Cγ(H)(R″)} (μ-CO)(CO)(Cp)2] (R″ = CO2Me, R′ = H, 3a; R″ = CN, R′ = H, 3b; R″ = C6H5, R′ = H, 3c; R″ = R′ = CO2Et, 3d). The coupling reaction of olefin with thiocarbyne is regio- and stereospecific, leading to the formation of only one isomer. C-C bond formation occurs between the less substituted alkene carbon and the thiocarbyne. Moreover, olefinic hydrogens of the bridging ligands are mutually trans.The reactions of 3a-b with MeSO3CF3 result, selectively, in the formation of the cationic μ-sulphonium allylidene complexes [Fe2{μ-η1:η3-Cα(SMe2)Cβ (H)Cγ(H)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = CO2Me, 4a; R = CN, 4b). Compound 4a undergoes displacement of the SMe2 group by nucleophiles such as NaBH4, NBu4CN and NaOMe, affording the complexes [Fe2{μ-η1:η3-Cα(R)Cβ (H)Cγ(H)(CO2Me)}(μ-CO)(CO)(Cp)2] (R = H, 5a; R = CN, 5b; R = OMe, 5c), respectively. The molecular structures of 3a and 5a have been determined by X-ray diffraction studies. 相似文献
15.
Reactions of 0.5 eq. of the dinuclear complexes [(η6-arene)Ru(μ-Cl)Cl]2 (arene = η6-C6H6, η6-p-iPrC6H4Me) and [(Cp∗)M(μ-Cl)Cl]2 (M = Rh, Ir; Cp∗ = η5-C5Me5) with 4,6-disubstituted pyrazolyl-pyrimidine ligands (L) viz. 4,6-bis(pyrazolyl)pyrimidine (L1), 4,6-bis(3-methyl-pyrazolyl)pyrimidine (L2), 4,6-bis(3,5-dimethyl-pyrazolyl)pyrimidine (L3) lead to the formation of the cationic mononuclear complexes [(η6-C6H6)Ru(L)Cl]+ (L = L1, 1; L2, 2; L3, 3), [(η6-p-iPrC6H4Me)Ru(L)Cl]+ (L = L1, 4; L2, 5; L3, 6), [(Cp∗)Rh(L)Cl]+ (L = L1, 7; L2, 8; L3, 9) and [(Cp∗)Ir(L)Cl]+ (L = L1, 10; L2, 11; L3, 12), while reactions with 1.0 eq. of the dinuclear complexes [(η6-arene)Ru(μ-Cl)Cl]2 and [(Cp∗)M(μ-Cl)Cl]2 give rise to the dicationic dinuclear complexes [{(η6-C6H6)RuCl}2(L)]2+ (L = L1, 13; L2, 14; L3, 15), [{(η6-p-iPrC6H4Me)RuCl}2(L)]2+ (L = L1, 16; L2, 17; L3, 18), [{(Cp∗)RhCl}2(L)]2+ (L = L1, 19; L2, 20; L3, 21) and [{(Cp∗)IrCl}2(L)]2+ (L = L1 22; L2, 23; L3 24). The molecular structures of [3]PF6, [6]PF6, [7]PF6 and [18](PF6)2 have been established by single crystal X-ray structure analysis. 相似文献
16.
Natalia P. Kuzmina Dmitry M. Tsymbarenko Igor E. Korsakov Zoya A. Starikova Kostantin A. Lysenko Olga V. Boytsova Andrey V. Mironov Irina P. Malkerova Andrey S. Alikhanyan 《Polyhedron》2008
The novel mixed ligand complexes [Ca(hfa)2(diglyme)(H2O)] (I), [Sr(hfa)2(diglyme)(H2O)] (II) and [Ba(hfa)2(diglyme)2] (III) (Hhfa = 1,1,1,5,5,5-hexafluoropentane-2,4-dione, diglyme = 2,5,8-trioxanonane) were synthesized by the reactions of the alkaline earth element (AEE) carbonates in n-hexane with a mixture of Hhfa and diglyme, and they were characterized by elemental analysis, 1H and 13C NMR, and FTIR spectroscopy. The crystal structures of I–III, consisting of mononuclear isolated molecules, have been determined. The thermal behavior and composition of the vapor phase have been studied for I–III by thermal analysis at low pressure and mass spectrometry using a Knudsen cell. The stability of the mixed ligand complexes [M(hfa)2(diglyme)n] to the removal of diglyme molecules under heating decreases in the row I > II ≈ III, and only I evaporates as the mixed ligand complex after water removal. 相似文献
17.
Luigi Busetto 《Journal of organometallic chemistry》2008,693(1):57-67
The bridging aminocarbyne complexes [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)2(Cp)2][SO3CF3] (R = Me, 1a; Xyl, 1b; 4-C6H4OMe, 1c; Xyl = 2,6-Me2C6 H3) react with acrylonitrile or methyl acrylate, in the presence of Me3NO and NaH, to give the corresponding μ-allylidene complexes [Fe2{μ-η1:η3- Cα(N(Me)(R))Cβ(H)Cγ(H)(R′)}(μ-CO)(CO)(Cp)2] (R = Me, R′ = CN, 3a; R = Xyl, R′ = CN, 3b; R = 4-C6H4OMe, R′ = CN, 3c; R = Me, R′ = CO2Me, 3d; R = 4-C6H4OMe, R′ = CO2Me, 3e). Likewise, 1a reacts with styrene or diethyl maleate, under the same reaction conditions, affording the complexes [Fe2{μ-η1:η3-Cα(NMe2)Cβ(R′)Cγ(H)(R″)}(μ-CO)(CO)(Cp)2] (R′ = H, R″ = C6H5, 3f; R′ = R″ = CO2Et, 3g). The corresponding reactions of [Ru2{μ-CN(Me)(CH2Ph)}(μ-CO)(CO)2(Cp)2][SO3CF3] (1d) with acrylonitrile or methyl acrylate afford the complexes [Ru2{μ-η1:η3-Cα(N(Me)(CH2Ph))Cβ(H)Cγ(H)(R′)}(μ-CO)(CO)(Cp)2] (R′ = CN, 3h; CO2Me, 3i), respectively.The coupling reaction of olefin with the carbyne carbon is regio- and stereospecific, leading to the formation of only one isomer. C-C bond formation occurs selectively between the less substituted alkene carbon and the aminocarbyne, and the Cβ-H, Cγ-H hydrogen atoms are mutually trans.The reactions with acrylonitrile, leading to 3a-c and 3h involve, as intermediate species, the nitrile complexes [M2{μ-CN(Me)(R)}(μ-CO)(CO)(NC-CHCH2)(Cp)2][SO3CF3] (M = Fe, R = Me, 4a; M = Fe, R = Xyl, 4b; M = Fe, R = 4-C6H4OMe, 4c; M = Ru, R = CH2C6H5, 4d).Compounds 3a, 3d and 3f undergo methylation (by CH3SO3CF3) and protonation (by HSO3CF3) at the nitrogen atom, leading to the formation of the cationic complexes [Fe2{μ-η1:η3-Cα(N(Me)3)Cβ(H)Cγ(H)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = CN, 5a; R = CO2Me, 5b; R = C6H5, 5c) and [Fe2{μ-η1:η3-Cα(N(H)(Me)2)Cβ(H)Cγ(H)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = CN, 6a; R = CO2Me, 6b; R = C6H5, 6c), respectively.Complex 3a, adds the fragment [Fe(CO)2(THF)(Cp)]+, through the nitrile functionality of the bridging ligand, leading to the formation of the complex [Fe2{μ-η1:η3-Cα(NMe2)Cβ(H)Cγ(H)(CNFe(CO)2Cp)}(μ-CO)(CO)(Cp)2][SO3CF3] (9).In an analogous reaction, 3a and [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)2(Cp)2][SO3CF3], in the presence of Me3NO, are assembled to give the tetrameric species [Fe2{μ-η1:η3-Cα(NMe2)Cβ(H)Cγ(H)(CN[Fe2{μ- CN(Me)(R)}(μ-CO)(CO)(Cp)2])}(μ-CO)(CO)(Cp)2][SO3CF3] (R = Me, 10a; R = Xyl, 10b; R = 4-C6H4OMe, 10c).The molecular structures of 3a and 3b have been determined by X-ray diffraction studies. 相似文献
18.
Ya-Hui Zhao Zhong-Min SuYao-Mei Fu Kui-Zhan ShaoPeng Li Yong WangXiang-Rong Hao Dong-Xia ZhuSi-Dong Liu 《Polyhedron》2008
A series of metal-organic frameworks, namely [Ni(PDB)(H2O)]n (1), [Pb(PDB)(H2O)] · (H2O) (2), [Co2(PDB)2(bpy)2(H2O)4] · 4H2O (3) and [Co2(PDB)2(phen)2]n (4) (H2PDB = pyridine-3,5-dicarboxylic acid, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized based on pyridine-3,5-dicarboxylate acid and two neutral chelate ligands, with different metal ions such as NiII, CoII and PbII, under hydrothermal conditions. The framework structures of these polymeric complexes have been determined by the X-ray single crystal diffraction technique. In the four complexes, the pyridine-3,5-dicarboxylate acid ligand exhibits diverse coordination modes, which play an important role in the construction of metal-organic frameworks. The thermal analyses of these four complexes have been measured and discussed. In addition, complex 2 shows strong phosphorescent emission at room temperature and the magnetic measurement of the polymer of 4 reveals a typical antiferromagnetic exchange. 相似文献
19.
Manuel Gómez Pilar Gómez-Sal José Manuel Hernández 《Journal of organometallic chemistry》2007,692(11):2291-2298
Trichloro methyl [Nb{η5-C5H3(SiXMe2)(SiMe3)}Cl3Me] (X = Cl, 2; Me, 3), dichloro dimethyl [Nb{η5-C5H3(SiXMe2)(SiMe3)}Cl2Me2] (X = Cl, 4; Me, 5) and tetramethyl [Nb{η5-C5H3(SiXMe2)(SiMe3)}Me4] (X = Me, 6; Cl, 7) niobium complexes were synthesized by treatment of starting tetrachloro derivatives [Nb{η5-C5H3(SiXMe2)(SiMe3)}Cl4] (X = Cl, 1a; Me, 1b) with dimethyl zinc or chloro methyl magnesium in different proportions and conditions. A mixture of trichloro methyl and dichloro dimethyl tantalum complexes [Ta{η5-C5H3(SiClMe2)(SiMe3)}Cl4−xMex] (x = 1, 8; 2, 9) in a 2:1 molar ratio was obtained in the reaction of [Ta{η5-C5H3(SiClMe2)(SiMe3)}Cl4] (1c) with 0.5 equivalents of ZnMe2 in toluene at low temperature. 8 could be isolated as single compound when 1 equivalent of 1c was added to the mixtures of 8 and 9, while the reaction of 1c with 1.5 equivalents of dimethyl zinc gave 9 as unitary product. However, [Ta{η5-C5H3(SiMe3)2}Cl4] (1d) reacts with 0.5 equivalents of alkylating reagent giving the trichloro methyl compound [Ta{η5-C5H3(SiMe3)2}Cl3Me] (10) in good yield. On the other hand, [Ta{η5-C5H3(SiMe3)2}Cl4] (1d) reacts with 2 equivalents of MgClMe in hexane at room temperature giving a mixture of dichloro dimethyl and chloro trimethyl complexes[Ta{η5-C5H3(SiMe3)2}Cl4−xMex] (x = 2, 11; 3, 12), while the use of 4 equivalents of MgClMe converts 1c into the tetramethyl derivative [Ta{η5-C5H3(SiClMe2)(SiMe3)}Me4] (13). Finally, a tetramethyl tantalum complex [Ta{η5-C5H3(SiMe3)2}Me4] (14) was prepared by reaction of [Ta{η5-C5H3(SiXMe2)(SiMe3)}Cl4] (X = Cl, 1c; Me, 1d) with 5 (X = Cl) or 4 (X = Me) equivalents of MgClMe in diethyl ether (X = Cl) or hexane (X = Me), respectively, as solvent. All the complexes were studied by IR and NMR spectroscopy and the molecular structure of the complex 11 was determined by X-ray diffraction methods. 相似文献
20.
R. Hernández-Molina I. Kalinina P. Esparza M. Sokolov J. Gonzalez-Platas A. Estévez-Braun E. Pérez-Sacau 《Polyhedron》2007
Complexes of naturally occurring hydroxynaphtho-quinone, lapachol (2-hydroxy-3(3-methyl-2-buthenyl)-1,4-naphthoquinone = HL) with Co(II), Ni(II) and Cu(II) have been prepared by reaction of the corresponding acetates with the ligand (HL) in ethanol. The molecular and crystal structures were determined for [CoL2(EtOH)2] (1), [NiL2(EtOH)2] (2), and [CuL2(py)2] (3). In all cases the deprotonated lapachol behaves as chelating bidentate ligand. The complexes were also characterized by elemental analyses, cyclic voltammetry, and FAB-MS. 相似文献