共查询到20条相似文献,搜索用时 46 毫秒
1.
Hans J. Breunig Tim Koehne Ana Maria Preda Cristian Silvestru Luis F. Piedra-Garza 《Journal of organometallic chemistry》2010,695(9):1307-1313
The syntheses and spectroscopic (NMR, MS) investigations of the antimonates [Ph4P]+[Me2SbCl4]− (1), [Me4Sb]+[Me2SbCl4]− (2), [Et4N]+[Ph2SbCl4]− (3), [Bu4N]+[Ph2SbCl4]− (4), [Me4Sb]+[Ph2SbCl4]− (5), [Et3MeSb]+[Ph2SbCl4]− (6), [Et4N]+[Ph2SbF4]− (7) and [Et4N]+[Ph2SbBr4]− (8) are reported. Halogen scrambling reactions of Et4NBr or Ph4EBr (E = P, Sb) with R2SbCl3 (R = Me, Ph) produce mixtures of compounds from which crystals of [Et4N]+[Ph2SbBr1.24Cl2.76]− (9), [Et4N]+[Ph2SbBr2.92Cl1.08]− (10) or [Ph4Sb]+[Me2SbCl4]− (11) were isolated. The crystal and molecular structures of 1 and 3-11 are reported. 相似文献
2.
William J. Evans Kevin A. Miller Wes R. Hillman Joseph W. Ziller 《Journal of organometallic chemistry》2007,692(17):3649-3654
The reductive reactivity of the (BPh4)1− ligand in pentamethylcyclopentadienyl [(C5Me5)2U][(μ-η2:η1-Ph)2BPh2] (1) was compared with that of the tetramethyl analog, [(C5Me4H)2U][(μ-η6:η1-Ph)(μ-η1:η1-Ph)BPh2] (2) using PhSSPh as a probe to determine if the mode of (BPh4)1− bonding affected the reduction. Both complexes act as two-electron reductants to form (C5Me4R)2U(SPh)2 [R = Me, 3; H, 4], but only in the R = H case could the product be crystallographically characterized. An improved synthesis of 1 from [(C5Me5)2UH]2 (5) and [Et3NH][BPh4] is also reported as well as its reaction with MeCN that provides another route to the unusual, parallel-ring, uranium metallocene [(C5Me5)2U(NCMe)5][BPh4]2 (6). 相似文献
3.
José Martínez-Lillo Lise-Marie Chamoreau Anna Proust Michel Verdaguer Pierre Gouzerh 《Comptes Rendus Chimie》2012,15(10):889-894
Four novel hexanuclear manganese(III) complexes based on derivatized salicylamidoximes, [MnIII6(μ3-O)2(O2CPh)2(Me2N-sao)6(EtOH)4] (1), [MnIII6(μ3-O)2(O2CPh)2(Me2N-sao)6(iPrOH)4] (2), [MnIII6(μ3-O)2(O2CPh)2(Et2N-sao)6(EtOH)4] (3) and [MnIII6(μ3-O)2(O2CPh)2(Et2N-sao)6(iPrOH)4] (4) (Me2N-Hsao = dimethylsalicylamidoxime; Et2N-Hsao = diethylsalicylamidoxime), have been prepared and characterized. Single-crystal X-ray diffraction allows one to determine that 1·2CHCl3 and 4 crystallize in the triclinic system with space group P(–1), whereas 3 crystallizes in the monoclinic system with space group P21/n. dc and ac magnetic susceptibility measurements of 1-4 reveal ferromagnetic coupling between Mn(III) metal ions and single-molecule magnet behaviour. The anisotropy barriers are 56, 52, 71 and 59 K for 1, 2, 3 and 4, respectively. 相似文献
4.
The reactions of Pt2Me4(μ-SMe2)2 and [ReS4]− in MeCN solution have been investigated. The resulting polyalkylated clusters: Et4N[ReS4PtMe2] (Et4N[1]), Et4N[ReS4(PtMe2)2] (Et4N[2]), and Et4N[ReS4(PtMe2)4] (Et4N[4]), were characterized by 1H, 13C, 195Pt NMR spectroscopy and ESI mass spectrometry. The structure of Et4N[1] was confirmed by single crystal X-ray diffraction, which demonstrated the expected square planar and tetrahedral coordination spheres bridged by a pair of sulfur atoms. 相似文献
5.
The reaction of the complex [{(η6-C6Me6)Ru(μ-Cl)Cl}2] 1 with sodium azide ligand gave two new dimers of the composition [{(η6-C6Me6)Ru(μ-N3)(N3)}2] 2 and [{(η6-C6Me6)Ru(μ-N3)Cl}2] 3, depending upon the reaction conditions. Complex 3 with excess of sodium azide in ethanol yielded complex 2. These complexes undergo substitution reactions with monodentate ligands to yield monomeric complexes of the type [(η6-C6Me6)Ru(X)(N3)(L)] {X = N3, Cl, L = PPh3 (4a, 9a); PMe2Ph (4b, 9b); AsPh3 (4c, 9c); X = N3, L = pyrazole (Hpz) (5a); 3-methylpyrazole (3-Hmpz) (5b) and 3,5-dimethyl-pyrazole (3,5-Hdmpz) (5c)}. Complexes 2 and 3 also react with bidentate ligands to give bridging complexes of the type [{(η6-C6Me6)Ru(N3)(X)]2(μ-L)} {X = N3, Cl, L = 1,2-bis(diphenylphosphino)methane (dppm) (6, 10); 1,2-bis(diphenylphosphino)ethane (dppe) (7, 11); 1,2-bis(diphenylphosphino)propane (dppp) (8, 12); X = Cl, L = 4,4-bipyridine (4,4′-bipy) (13)}. These complexes were characterized by FT-IR and FT-NMR spectroscopy as well as by analytical data.The molecular structures of the representative complexes [{(η6-C6Me6)Ru(μ-N3)(N3)}2] 2, [{(η6-C6Me6)Ru(μ-N3)Cl}2] 3,[(η6-C6Me6)Ru(N3)2(PPh3)] 4a and [{(η6-C6Me6)Ru(N3)2}2 (μ-dppm)] 6 were established by single crystal X-ray diffraction studies. 相似文献
6.
Synthesis of bulky tris[(dimethyl(alkyl/aryl)silyl)methyl]stannanes as radical based reducing agents
The synthesis of novel bulky tris[dimethyl(ethyl/benzyl/p-tolyl/α-naphthyl)silylmethyl]stannanes (1-4) is described. Alkylation of SnCl4 with Me2(ethyl/p-tolyl)SiCH2MgBr (10-11) gave mainly the triorganotin chlorides [(Me2(ethyl/p-tolyl)SiCH2)]3SnCl 14 and 15, which were isolated by silica gel chromatography. Reduction of 14 and 15 with LiAlH4 in THF gave the corresponding triorganotin hydrides 1 and 2, respectively. [Me2(benzyl/α-naphthyl)SiCH2]3SnCl 16 and 17, generated by the alkylation of SnCl4 with Me2(benzyl/α-naphthyl)SiCH2MgBr 12 and 13, were inseparable from the minor product [Me2(benzyl/α-naphthyl)SiCH2]2SnCl218 and 19, respectively. Treatment of the mixtures of 16/18 and 17/19 with NaOH furnished the corresponding mixtures of stannoxanes, from which the hexakisdistannoxanes [Me2(benzyl/α-naphthyl)SiCH2]6Sn2O 20 and 22 were isolated from the minor dialkyltin oxide derivatives [Me2(benzyl/α-naphthyl)SiCH2]2SnO in good yields. Reduction of 20 and 22 with BH3 in THF gave [Me2(benzyl/α-naphthyl)SiCH2]3SnH (3 and 4), respectively in good yields. 1H, 13C, 119Sn, 29Si NMR characteristics of the newly synthesized compounds are included. 相似文献
7.
The mono(guanidinate) lanthanide borohydride complexes of [(Me3Si)2NC(NCy)2]Ln(BH4)2(THF)2 (Ln = Yb (1), Er (2)) have been synthesized by the reactions of corresponding Ln(BH4)3(THF)3 with sodium guanidinate of [(Me3Si)2NC(NCy)2]Na in a 1:1 molar ratio in THF. They were characterized by elemental analysis, infrared spectrum and X-ray diffraction analysis. 1 and 2 have similar structures. The lanthanide ion was bonded by an η2-guanidinate ligand, two η3-BH4 ligands and two THF molecules as a distorted octahedron. The two BH4 ligands in a complex are equivalent and cis to each other. The structure of solvated sodium guanidinate of {[(Me3Si)2NC(NCy)2]Na(THF)}2 (3) was also presented. In a dimeric molecule of 3, each Na atom is bound to three nitrogen atoms from two guanidinate groups and one oxygen atom from the THF molecule. 1 and 2 displayed moderate high catalytic activity for the polymerization of methyl methacrylate. The Er complex is more active than the Yb complex. 相似文献
8.
Reduction of isopropyldimethylsilyl-substituted titanocene dichloride [TiCl2(η5-C5Me4SiMe2Pri)2] (1) by excess magnesium in the presence of excess bis(trimethylsilyl)ethyne (btmse) in tetrahydrofuran at 60 °C yielded a mixture of products amongst them only the trinuclear Ti-Mg-Ti hydrido-bridged complex Mg[Ti(μ-H)2(η5-C5Me4SiMe2Pri)]2 (3) was isolated and characterized. The precursor of titanocene, [Ti(η5-C5Me4SiMe2Pri)2(η2-btmse)] (6), was obtained from the identical system which, after initial formation of [TiCl(η5-C5Me4SiMe2Pri)2] (2), reacted at −18 °C overnight and then the solution was rapidly separated from the remaining magnesium. Titanocene [Ti(η5-C5Me4SiMe2Pri)2] (7) was obtained by thermolysis of 6 at 75 °C in vacuum. Crystal structures of 1, 2, 3, 6, and 7 were determined. 相似文献
9.
Xiao-Yi Yi Qian-Feng Zhang Wa-Hung Leung 《Journal of organometallic chemistry》2009,694(26):4256-4260
Interaction of [LOEtZrF3] ( = [Co(η5-C5H5){P(O)(OEt)2}3]−) (1) with 3 equivalents of bis(trimethylsilyl) sulfate afforded the ZrIV hydrogensulfato complex [(LOEt)2Zr2(SO4)2(HSO4)2] (2) that reacted with Et3N to give [Et3NH][LOEtZr(H2O)(SO4)2] (3). Treatment of complex 1 with 3 equivalents of trimethylsilyl acetate afforded [LOEtZr(OCOCH3)3] (4), whereas that with 1 and 2 equivalents of trimethylsilyl trimethylsiloxyacetate yielded [LOEtZrF(OCOCH2O)]2 (5) and [LOEtZr(OCOCH2OH)(OCOCH2O)]2 (6), respectively. The crystal structures of complexes 2 and 6 have been determined. 相似文献
10.
Alpar Pöllnitz Anca Silvestru Cristian Silvestru 《Journal of organometallic chemistry》2010,695(23):2486-2492
Diorganodiselenide [2-(Et2NCH2)C6H4]2Se2 (1) was obtained by hydrolysis/oxidation of the corresponding [2-(Et2NCH2)C6H4]SeLi derivative. The treatment of [2-(Et2NCH2)C6H4]2Se2 with elemental sodium in THF resulted in [2-(Et2NCH2)C6H4]SeNa (2). Reactions between alkali metal selenolates [2-(R2NCH2)C6H4]SeM′ (R = Me, Et; M′ = Li, Na) and MCl2 (M = Zn, Cd) in a 2:1 molar ratio resulted in the [2-(R2NCH2)C6H4Se]2M species [R = Me, M = Zn (3), Cd (4); R = Et, M = Zn (5), Cd (6)]. The new compounds were characterized by multinuclear NMR (1H, 13C, 77Se, 113Cd) and mass spectrometry. The crystal and molecular structures of 1, 3 and 4 revealed monomeric species stabilized by N → Se (for 1) and N → M (for 3 and 4) intramolecular interactions. 相似文献
11.
Almudena García-Fernández Josefina Díez Ángel Manteca Jesús Sánchez M. Pilar Gamasa Elena Lastra 《Polyhedron》2008
A series of half-sandwich ruthenium(II) complexes containing κ3(N,N,N)-hydridotris(pyrazolyl)borate (κ3(N,N,N)-Tp) and the water-soluble phosphane 1,3,5-triaza-7-phosphaadamantane (PTA) [RuX{κ3(N,N,N)-Tp}(PPh3)2−n(PTA)n] (n = 2, X = Cl (1), n = 1, X = Cl (2), I (3), NCS (4), H (5)) and [Ru{κ3(N,N,N)-Tp}(PPh3)(PTA)L][PF6] (L = NCMe (6), PTA (7)) have been synthesized. Complexes containing 1-methyl-3,5-diaza-1-azonia-7-phosphaadamantane(m-PTA) triflate [RuCl{κ3(N,N,N)-Tp}(m-PTA)2][CF3SO3]2 (8) and [RuX{κ3(N,N,N)-Tp}(PPh3)(m-PTA)][CF3SO3] (X = Cl (9), H (10)) have been obtained by treatment, respectively, of complexes 1, 2 and 5 with methyl triflate. Single crystal X-ray diffraction analysis for complexes 1, 2 and 4 have been carried out. DNA binding properties by using a mobility shift assay and antimicrobial activity of selected complexes have been evaluated. 相似文献
12.
Philip C. Andrews Craig M. Forsyth Peter C. Junk Iryna Nuzhnaya Leone Spiccia 《Journal of organometallic chemistry》2009,694(3):373-381
The treatment of InCl3 with MOCH(CF3)2 (M = Li, Na, K) in a 1:6 stoichiometry, followed by recrystallisation results in the formation of the bimetallic “ate” complexes [Na3In(OCH(CF3)2)6(THF)3] (2) and [Li3In(OCH(CF3)2)6(THF)3] (5) from hexane, and [K3In(OCH(CF3)2)6]n (4) from a THF and toluene mixture. If a 1:3 stoichiometry is used chloride containing compounds [Na2InCl(OCH(CF3)2)4(THF)4] (1) and [KInCl2 (OCH(CF3)2)2(THF)3]n · THF (3) are obtained on recrystallisation from hexane. Treatment of GaCl3 with 6 equivalents of LiOC(CH3)2CF3 gives [LiGa(OC(CH3)2CF3)4(THF)2] (6) on recrystallisation from hexane. The protolysis reaction between In(N(SiMe3)2)3, formed in situ from (Me3Si)2NH, nBuLi and Incl3, and HOCH(CH3)CF3 results in isolation of [LiIn(OCH(CH3)CF3)3Bu]2 (7) from hexane. The structures of 2, 4, and 5 all contain the tetranuclear core InO6M3. Compounds 1 and 3 have residual chloride; 1 is a trinuclear species with two THF ligands per Na, while 3 is a linear polymer. Compound 6 has a GaO2Li four-membered parallelogram at its core. Complex 7 has a tetranuclear In2O6Li2 core and an unexpected nBu group on the In atoms. The coordination spheres of the alkali metals in 1-6 include solvated THF while 1-5 display additional close M?F interactions. 相似文献
13.
The reactions of trans-[MoO(ONOMe)Cl2] 1 (ONOMe = methylamino-N,N-bis(2-methylene-4,6-dimethylphenolate) dianion) and trans-[MoO(ONOtBu)Cl2] 2 (ONOtBu = methylamino-N,N-bis(2-methylene-4-methyl-6-tert-butylphenolate) dianion) with PhNCO afforded new imido molybdenum complexes trans-[Mo(NPh)(ONOMe)Cl2] 3 and trans-[Mo(NPh)(ONOtBu)Cl2] 4, respectively. As analogous oxotungsten starting materials did not show similar reactivity, corresponding imido tungsten complexes were prepared by the reaction between [W(NPh)Cl4] with aminobis(phenol)s. These reactions yielded cis- and trans-isomers of dichloro complexes [W(NPh)(ONOMe)Cl2] 5 and [W(NPh)(ONOtBu)Cl2] 6, respectively. The molecular structures of 4, cis-6 and trans-6 were verified by X-ray crystallography. Organosubstituted imido tungsten(VI) complex cis-[W(NPh)(ONOtBu)Me2] 7 was prepared by the transmetallation reaction of 6 (either cis or trans isomer) with methyl magnesium iodide. 相似文献
14.
Miao-Hsing Hsu 《Journal of organometallic chemistry》2006,691(5):966-974
A facile synthesis of the novel selenium-capped trimolybdenum and tritungsten ring carbonyl clusters [Se2M3(CO)10]2− (M = Mo, 1; W, 4) have been achieved. The selenium-capped trimolybdenum cluster compound [Et4N]2[Se2Mo3(CO)10] ([Et4N]2[1]) can be obtained from the reaction of the trichromium cluster compound [Et4N]2[Se2Cr3(CO)10] with 4 equiv. of Mo(CO)6 in refluxing acetone. On the other hand, when [Et4N]2[Se2Cr3(CO)10] reacted with 4 equiv. of W(CO)6 in refluxing acetone, the planar cluster compound [Et4N]2[Se2W4(CO)18] ([Et4N]2[3]) was isolated, which could further transform to the tritungsten cluster compound [Et4N]2[Se2W3(CO)10] ([Et4N]2[4]) in good yield. Alternatively, clusters 1 and 4 could be formed from the reactions of the monosubstituted products [Et4N]2[Se2Cr2M(CO)10] (M = Mo; W, [Et4N]2[2]) with 3 equiv. of M(CO)6 in acetone, respectively. Complexes 1-4 are fully characterized by IR, 77Se NMR spectroscopy, and single-crystal X-ray analysis. Clusters 1, 2, and 4 are isostructural and each display a trigonal bipyramidal structure with a homometallic M3 ring (M = Mo, 1; W, 4) or a heterometallic Cr2W ring that is further capped above and below by μ3-Se atoms. Further, the intermediate planar complex 3 exhibits a Se2W2 square with each Se atom externally coordinated to one W(CO)5 group. This paper describes a systematic route to a series of selenium-capped trimetallic carbonyl clusters and the formation and the structural features of the resultant clusters are discussed. 相似文献
15.
Ronald Lindner Goran N. Kaluđerović Reinhard Paschke Christoph Wagner Dirk Steinborn 《Polyhedron》2008
Reactions of [PtMe3(OCMe2)3](BF4) and [(PtMe3I)4] with pyrazole (pzH) afforded mononuclear pyrazole platinum(IV) complexes [PtMe3(pzH)3](BF4) (1) and [PtMe3I(pzH)2] (2), respectively. The formation of dinuclear pyrazolato bridged platinum(IV) complexes (PPN)[(PtMe3)2(μ-pz)3] (3), (PPN)[(PtMe3)2(μ-I)(μ-pz)2] · 1/2Et2O (4) and [K(18C6)][(PtMe3)2(μ-I)(μ-pz)2] (5) was achieved by the reaction of each 1 and 2 with [PtMe3(OCMe2)3](BF4) in the presence of KOAc followed by reaction with (PPN)Cl (PPN+ = bis(triphenylphosphine)iminium cation) and 18C6, respectively. The reaction of complex 4 with AgO2CCF3 followed by addition of RSR′ (R/R′ = Me/Me, Me/Ph) resulted in the formation of complexes [(PtMe3)2(μ-pz)2(μ-RSR′)] (R/R′ = Me/Me, 6; Me/Ph, 7). All complexes were characterized unambiguously by microanalysis and NMR (1H, 13C) spectroscopic investigations. Additionally, crystal structures of complexes 3 and 4 as well as DFT calculation are presented. Furthermore, in vitro studies on the anti-proliferative activity of complexes 2 and 5 were carried out. 相似文献
16.
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
17.
Susie Douglas Mary F. Mahon Michael K. Whittlesey 《Journal of organometallic chemistry》2005,690(23):5027-5035
Addition of excesses of N-heterocyclic carbenes (NHCs) IEt2Me2, IiPr2Me2 or ICy (IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene; IiPr2Me2 = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene; ICy = 1,3-dicyclohexylimidazol-2-ylidene) to [HRh(PPh3)4] (1) affords an isomeric mixture of [HRh(NHC)(PPh3)2] (NHC = IEt2Me2 (cis-/trans-2), IiPr2Me2 (cis-/trans-3), ICy (cis-/trans-4) and [HRh(NHC)2(PPh3)] (IEt2Me2(cis-/trans-5), IiPr2Me2 (cis-/trans-6), ICy (cis-/trans-7)). Thermolysis of 1 with the aryl substituted NHC, 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene (IMesH2), affords the bridging hydrido phosphido dimer, [{(PPh3)2Rh}2(μ-H)(μ-PPh2)] (8), which is also the reaction product formed in the absence of carbene. When the rhodium precursor was changed from 1 to [HRh(CO)(PPh3)3] (9) and treated with either IMes (=1,3-dimesitylimidazol-2-ylidene) or ICy, the bis-NHC complexes trans-[HRh(CO)(IMes)2] (10) and trans-[HRh(CO)(ICy)2] (11) were formed. In contrast, the reaction of 9 with IiPr2Me2 gave [HRh(CO)(IiPr2Me2)2] (cis-/trans-12) and the unusual unsymmetrical dimer, [(PPh3)2Rh(μ-CO)2Rh(IiPr2Me2)2] (13). The complexes trans-3, 8, 10 and 13 have been structurally characterised. 相似文献
18.
Paloma Paredes 《Journal of organometallic chemistry》2008,693(24):3681-3687
The treatment of the complex [Ir(η2-C2H4)2(L)][PF6] (L = κ3-N,N,N-(S,S)-iPr-pybox) with acetic acid (1:1 molar ratio) at −10 °C affords the complex [Ir(C2H5)(κ2-O,O-O2CCH3)(L)][PF6] (1). The dinuclear iridium(III) complex [Ir2(μ-Cl)2(C2H5)2(L)2][PF6]2 (2) is stereoselectively obtained by spontaneous intramolecular insertion of ethylene into the iridium-hydride bond of the mononuclear complex [IrClH(η2-C2H4)(L)][PF6]. The single bridging chloride dinuclear derivative [Ir2(μ-Cl)(C2H5)2Cl2(L)2][PF6] (3) is prepared by reaction of 2 with one equivalent of NaCl. The intramolecular insertion reaction of methyl and ethyl propiolate into the Ir-H bond of the complex [IrClH(MeCN)(L)][PF6] gives stereoselectively the dinuclear complexes [Ir2(μ-Cl)2(HCCHCO2R)2(L)2][PF6]2 (R = Me (4), Et (5)). The reaction of the complexes 4, 5 with one equivalent of NaCl or with an excess of sodium acetate yields the dinuclear [Ir2(μ-Cl)(HCCHCO2R)2Cl2(L)2][PF6] (R = Me (6), Et (7)) or the mononuclear [IrCl(HCCHCO2Et)(κ1-O-O2CMe)(L)] (8) complexes, respectively. The structure of the dinuclear complex 3 · CH2Cl2 has been determined by an X-ray monocrystal study. 相似文献
19.
Verena Schnitzler 《Journal of organometallic chemistry》2008,693(15):2610-2614
Reaction of 3,4-dimethylphospholylthallium (Tl-1) with [Cp∗MCl2]2 (M = Rh, Ir) leads to the formation of the dimeric species [(Cp∗M)2(Me2C4H2P)3]+2 and 3 with bridging μ-η1:η1-phospholyl ligands. The phosphametallocenium sandwich complexes [Cp∗M(Me2C4(SiMe3)2P)]+7 (M = Rh) and 8 (M = Ir) could be obtained from the reaction of [Cp∗MCl2]2 and the 2,5-bis(trimethylsilyl)-1-trimethylstannylphosphole 6, with the bulky trimethylsilyl groups preventing the phosphole from η1- and enforcing a η5-coordination. The structures of phospharhodocenium cation 7 and a byproduct 9 containing a phosphairidocenium moiety could be determined by X-ray diffraction. 相似文献
20.
Reactions of [Fe2(CO)6(μ-pdt)] (1) (pdt = SCH2CH2CH2S) and small bite-angle diphosphines have been studied. A range of products can be formed being dependent upon the nature of the diphosphine and reaction conditions. With bis(diphenylphosphino)methane (dppm), thermolysis in toluene leads to the formation of a mixture of bridge and chelate isomers [Fe2(CO)4(μ-dppm)(μ-pdt)] (2) and [Fe2(CO)4(κ2-dppm)(μ-pdt)] (3), respectively. Both have been crystallographically characterised, 3 being a rare example of a chelating dppm ligand in a first row binuclear system. At room temperature in MeCN with added Me3NO · 2H2O, the monodentate complex [Fe2(CO)5(κ1-dppm)(μ-pdt)] (4) is initially formed. Warming 4 to 100 °C leads the slow conversion to 2, while oxidation (on alumina) gives [Fe2(CO)5(κ1-dppmO)(μ-pdt)] (5). With bis(dicyclohexylphosphino)methane (dcpm), heating in toluene cleanly affords [Fe2(CO)4(μ-dcpm)(μ-pdt)] (6). With Me3NO · 2H2O in MeCN the reaction is not clean as the phosphine is oxidised but monodentate [Fe2(CO)5(κ1-dcpm)(μ-pdt)] (7) can be seen spectroscopically. With 1,2-bis(diphenylphosphino)benzene (dppb) and cis-1,2-bis(diphenylphosphino)ethene (dppv) the chelate complexes [Fe2(CO)4(κ2-dppb)(μ-pdt)] (8) and [Fe2(CO)4(κ2-dppv)(μ-pdt)] (9), respectively are the final products under all conditions, although a small amount of [Fe2(CO)5(κ2-dppvO)(μ-pdt)] (10) was also isolated. Protonation of 2 with HBF4 affords a cation with poor stability while with the more basic diiron centre in 6 readily forms the stable bridging-hydride complex [(μ-H)Fe2(CO)4(μ-dcpm)(μ-pdt)][BF4] (11) which has been crystallographically characterised. 相似文献