首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
The hydrothermal reactions of V2O5, HF and an organodiphosphonic acid, in the presence of appropriate templating organoammonium or metal-organic complex cations provided three new oxyfluorovanadate compounds. The V(IV) species [H3N(CH2)2NH2(CH2)2NH2(CH2)2NH3][V3O3F2(H2O){O3PCH2PO3}2]·2H2O (1·2H2O) exhibits a three-dimensional anionic framework constructed from {VO(O3PCH2PO3)}n2n chains and {VF2O4} octahedra. The molecular structure of [N(CH2CH2NH3)3]2[NH4][V3O2F6(O3PCH2PO3)2]·2H2O (2·2H2O) is characterized by the presence of unique {V3O2F6(O3PCH2PO3)2}7− clusters. The bimetallic phase [{Cu(ophen)}VOF{HO3P(CH2)5PO3}] (3) is one-dimensional with {Cu2V2O2F2(HO3PR)2(O3PR)2} cluster building blocks.  相似文献   

2.
Seven additional components, polyoxins C, D, E, F, G, H and I were isolated from polyoxin complex. They have molecular formulae corresponding to C11H15N3O8, C17H23N5O14, C17H23N5O13, C23H30N6O15, C17H25N5O12, C23H32N6O13 and C19H24N4O12, respectively. These polyoxins except inactive polyoxins C and I were highly active against various kinds of phytopathogenic fungi. The close structural similarity among them including polyoxins A and B is also discussed.  相似文献   

3.
A series of inorganic-organic hybrid compounds built from bis(undecatungstophosphate) lanthanates and copper-complexes, namely, H8[Cu(en)2H2O]4[Cu(en)2]{[Cu(en)2][La(PW11O39)2]}2·18H2O (1), H6[Na2(en)2(H2O)5][Cu(en)2H2O]4[Cu(en)2]{[Cu(en)2][Ce(PW11O39)2]}2·16H2O (2), H6[Na2(en)2(H2O)5][Cu(en)2H2O]4[Cu(en)2]{[Cu(en)2][Pr(PW11O39)2]}2·18H2O (3), H6[Na2(en)2(H2O)4][Cu(en)2H2O]4[Cu(en)2]{[Cu(en)2][Nd(PW11O39)2]}2·14H2O (4), H6[Na2(en)2(H2O)5][Cu(en)2H2O]4[Cu(en)2]{[Cu(en)2][Sm(PW11O39)2]}2·20H2O (5), and H7[Cu(en)2]2[Sm(PW11O39)2]·10H2O (6) (where en = 1,2-ethylenediamine), have been prepared. In these compounds, two lacunary [PW11O39]7− anions sandwich an eight-coordinated Ln(III) cation to yield [Ln(PW11O39)2]11− anion in a twisted square anti-prismatic geometry, which is further bridged by [Cu(en)2]2+ fragments to generate a 1D zigzag-like chain. In 1-6, the coordination bond interactions and weak interactions between adjacent 1D chains play an important role in the zigzagging distances and angles of different 1D chains. The magnetic studies indicate that antiferromagnetic interactions exist in compounds 1, 2 and 4.  相似文献   

4.
The preparation and characterisation of the complexes [Co2(CO)4(PMe3)2][Co2(CO)6](Me3SiC2C2SiMe3) (4), [Co2(CO)4(dppm)][Co2(CO)6](Me3SiC2C2H) (5), [Co2(CO)4(dppa)][Co2(CO)6](Me3SiC2C2SiMe3) (6), [Co2(CO)4(dppm)]2[Co2(CO)6](Me3SiC2CCC2C2SiMe3) (7) and [{SiMe3(Co2(CO)4(dppm))C2}2(HCC)(1,3,5-C6H3)] (8) are described. An electrochemical study of the complexes 5-8 and of the related [Co2(CO)4(dppm)]2(Me3SiC2(CC)2C2SiMe3) (1), [Co2(CO)4(dppa)]2(Me3SiC2C2SiMe3) (2) and [{SiMe3(Co2(CO)4(dppm))C2}(HCC)2(1,3,5-C6H3)] (3) is presented by means of the cyclic and square-wave voltammetry techniques. Crystals of 8 suitable for single-crystal X-ray diffraction were grown and the molecular structure of this compound is discussed.  相似文献   

5.
The influence of terminal ligands on the structure and nuclearity of copper(II)-pyrazolates has been investigated. Exchange of the chloride ligands of [Cu33-X)(μ-pz)3Cl3]n (X=O, OH; n=2, 1) or [Cu33-Cl)2(μ-pz)3Cl3]2− complexes for cyanate, acetate or bromide ligands maintains the integrity of the triangular species: PPN[Cu33-OH)(μ-pz)3(NCO)3], PPN[Cu33-OH)(μ-pz)3(O2CCH3)3(H2O)] · H2O, Bu4N[Cu33-OH)(μ-pz)3(O2CCH3)3] · 3H2O and (Bu4N)2[Cu33-Br)2(μ-pz)3Br3] have been prepared and characterized by spectroscopic and X-ray diffraction techniques, respectively. In contrast, tetranuclear complexes (Bu4N)2[Cu43-OH)2(μ-4-X-pz)2(μ-O2CPh)2(O2CPh)4] (X=H, Cl, Br, NO2) and the hexanuclear complex (Bu4N)2[Cu63-O)(μ3-OH)(μ-4-NO2-pz)6(μ-O2CPh)3(O2CPh)2(H2O)] · (CH2Cl2)0.5 have been obtained on substitution for benzoate ligands. An attempt to partially substitute the chlorides for tert-butoxide ligands, also provided a tetranuclear complex, (Bu4N)2[Cu4(μ-OH)2(μ-pz)4Cl4], without incorporation of the incoming ligand. Similarly, removal of all chloride ions in the absence of an appropriate substituting ligand leads to higher nuclearity metallacycles [Cu(μ-OH)(μ-pz)]n (n=6, 8, 9, 12, 14).  相似文献   

6.
The reactions of the Keplerate super cluster [Mo132O372(CH3CO2)30(H2O)72]42− with a Cu(II) source and an organonitrogen donor in methanol/DMF solutions yielded a series of bimetallic organic-inorganic oxide hybrid materials, including the molecular species [Cu(phen)2MoO4] (1) and [{Cu(terpy)}2(MoO4)2] (2) and a series of materials constructed from the tetranuclear building block {Mo4O10(OMe)6}2−: the molecular [{Cu2(phen)2(O2CCH3)2 (MeOH)}Mo4O10(OMe)6] (3), [{Cu(terpy)(O2CCH3)}2Mo4O10(OMe)6] (4) and [{Cu(terpy)Cl}2Mo4O10(OMe)6] (5), the one-dimensional phases [{Cu(bpy)(HOMe)2}Mo4O10(OMe)6] (6), [{Cu(bpy)(DMF)2}Mo4O10(OMe)6] (7), [{Cu(bpa)(DMF)2}Mo4O10(OMe)6] (8), [{Cu(phen)(DMF)2}Mo4O10(OMe)6] (9) and [{CuCl(dpa)}2Mo4O10(OMe)6] (10), and the two-dimensional material [{Cu2(DMF)2(pdpa)}{Mo4O10(OMe)6}2] (11). When methanol is replaced by the tridentate alkoxide tris-methoxypropane (trisp), the {Mo2O4(trisp)2}2− cluster building block is observed for [Cu(phen)Mo2O4(trisp)2] (12), [Cu(bpa)(DMF)Mo2O4(trisp)2] (13) and [{Cu(bpy)(NO3)}2Mo2O4(trisp)2] (14).  相似文献   

7.
The coordination chemistry of the metalloligand [Pt2(μ-S)2(PPh3)4] towards cobalt(II) and cobalt(III) centres has been explored using an electrospray ionisation mass spectrometry (ESI MS)-directed methodology. Reaction of [Pt2(μ-S)2(PPh3)4] with CoCl2·6H2O in methanol gave a green-yellow suspension of the known adduct [Pt2(μ-S)2(PPh3)4CoCl2], and the CoBr2 adduct could be similarly prepared. When in situ-generated [Pt2(μ-S)2(PPh3)4CoCl2] is reacted with 8-hydroxyquinoline (HQ) and base, the initial product is the cobalt(II) adduct [Pt2(μ-S)2(PPh3)4CoQ]+, which is then converted in air to the cobalt(III) adduct [Pt2(μ-S)2(PPh3)4CoQ2]+, isolated as its hexafluorophosphate salt. The corresponding picolinate (Pic) derivative [Pt2(μ-S)2(PPh3)4Co(Pic)2]+ was similarly prepared, however reaction of [Pt2(μ-S)2(PPh3)4], CoCl2·6H2O and 8-(tosylamino)quinoline (HTQ) produced only the cobalt(II) adduct [Pt2(μ-S)2(PPh3)4CoTQ]+. Reactions of [Pt2(μ-S)2(PPh3)4], CoCl2·6H2O and dithiocarbamates gave cobalt(III) complexes [Pt2(μ-S)2(PPh3)4Co(S2CNR2)2]+ [R = Et or R2 = (CH2)4], and proceeded much more rapidly, consistent with the known ability of the dithiocarbamate ligand to stabilize cobalt in higher oxidation states. A study of the fragmentation of cobalt(III) adducts by positive-ion ESI mass spectrometry indicated that [Pt2(μ-S)2(PPh3)4CoQ2]+ fragments to form the radical cation [Pt2(μ-S)2(PPh3)4]+, which could also be generated by ESI MS analysis of [Pt2(μ-S)2(PPh3)4] in methanol-NaOH solution. In contrast, the corresponding indium(III) derivative [Pt2(μ-S)2(PPh3)4InQ2]+, and the cobalt(III) dithiocarbamate [Pt2(μ-S)2(PPh3)4Co(S2CN(CH2)4)2]+ are much more reluctant to fragment under analogous conditions, and the differences are discussed in terms of cobalt(III) redox chemistry.  相似文献   

8.
Reactions of [Pt2(μ-S)2(PPh3)4] with the diarylthallium(III) bromides Ar2TlBr [Ar = Ph and p-ClC6H4] in methanol gave good yields of the thallium(III) adducts [Pt2(μ-S)2(PPh3)4TlAr2]+, isolated as their salts. The corresponding selenide complex [Pt2(μ-Se)2(PPh3)4TlPh2]BPh4 was similarly synthesised from [Pt2(μ-Se)2(PPh3)4], Ph2TlBr and NaBPh4. The reaction of [Pt2(μ-S)2(PPh3)4] with PhTlBr2 gave [Pt2(μ-S)2(PPh3)4TlBrPh]+, while reaction with TlBr3 gave the dibromothallium(III) adduct [Pt2(μ-S)2(PPh3)4TlBr2]+[TlBr4]. The latter complex is a rare example of a thallium(III) dihalide complex stabilised solely by sulfur donor ligands. X-ray crystal structure determinations on the complexes [Pt2(μ-S)2(PPh3)4TlPh2]BPh4, [Pt2(μ-S)2(PPh3)4TlBrPh]BPh4 and [Pt2(μ-S)2(PPh3)4TlBr2][TlBr4] reveal a greater interaction between the thallium(III) centre and the two sulfide ligands on stepwise replacement of Ph by Br, as indicated by shorter Tl-S and Pt?Tl distances, and an increasing S-Tl-S bond angle. Investigations of the ESI MS fragmentation behaviour of the thallium(III) complexes are reported.  相似文献   

9.
A series of arylantimony ferrocenylacrylates with the formula (C5H5FeC5H4CHCHCO2)nSbAr(5−n) (n=1, 2; Ar C6H5, 4-CH3C6H4, 3-CH3C6H4, 2-CH3C6H4, 4-FC6H4) have been synthesized and characterized by elemental analysis, IR, 1H NMR and mass spectra. The crystal structures of C5H5FeC5H4CHCHCO2Sb(C6H5)4 (I1) and (C5H5FeC5H4CHCHCO2)2Sb(C6H5)3 (II1) have been determined by X-ray diffraction.  相似文献   

10.
The reactions of [Pt2(μ-S)2(PPh3)4] with α,ω-dibromoalkanes Br(CH2)nBr (n = 4, 5, 6, 8, 12) gave mono-alkylated [Pt2(μ-S){μ-S(CH2)nBr}(PPh3)4]+ and/or di-alkylated [Pt2(μ-S(CH2)nS}(PPh3)4]2+ products, depending on the alkyl chain length and the reaction conditions. With longer chains (n = 8, 12), intramolecular di-alkylation does not proceed in refluxing methanol, with the mono-alkylated products [Pt2(μ-S){μ-S(CH2)nBr}(PPh3)4]+ being the dominant products when excess alkylating agent is used. The bridged complex [{Pt2(μ-S)2(PPh3)4}2{μ-(CH2)12}]2+ was accessible from the reaction of [Pt2(μ-S)2(PPh3)4] with 0.5 mol equivalents of Br(CH2)12Br. [Pt2(μ-S){μ-S(CH2)4Br}(PPh3)4]+ can be cleanly isolated as its BPh4 salt, but undergoes facile intramolecular di-alkylation at −18 °C, giving the known species [Pt2(μ-S(CH2)4S}(PPh3)4]2+. The reaction of I(CH2)6I with [Pt2(μ-S)2(PPh3)4] similarly gives [Pt2(μ-S){μ-S(CH2)6I}(PPh3)4]+, which is fairly stable towards intramolecular di-alkylation once isolated. These reactions provide a facile route to ω-haloalkylthiolate complexes which are poorly defined in the literature. X-ray crystal structures of [Pt2(μ-S){μ-S(CH2)5Br}(PPh3)4]BPh4 and [Pt2(μ-S(CH2)5S}(PPh3)4](BPh4)2 are reported, together with a study of these complexes by electrospray ionisation mass spectrometry. All complexes fragment by dissociation of PPh3 ligands, and the bromoalkylthiolate complexes show additional fragment ions [Pt2(μ-S){μ-S(CH2)n−2CHCH2}(PPh3)m]+ (m = 2 or 3; m ≠ 4), most significant for n = 4, formed by elimination of HBr.  相似文献   

11.
The reaction of [HRe3(CO)12]2− with an excess of Ph3PAuCl in CH2Cl2 yields [(Ph3PAu)4Re(CO)4]+ as the main product, which crystallizes as [(Ph3PAu)4Re(CO)4]PF6 · CH2Cl2 (1 · CH2Cl2) after the addition of KPF6.The crystal structure determination reveals a trigonal bipyramidal Au4Re cluster with the Re atom in equatorial position.If [(Ph3PAu)4Re(CO)4]+ is reacted with PPh4Cl, a cation [Ph3PAu]+ is eliminated as Ph3PAuCl, and the neutral cluster [(Ph3PAu)3Re(CO)4] (2) is formed.It combines with excess [(Ph3PAu)4Re(CO)4]+ to afford the cluster cation, [(Ph3PAu)6AuRe2(CO)8]+. It crystallizes from CH2Cl2 as[(Ph3PAu)6AuRe2(CO)8]PF6 · 4CH2Cl2 (3 · 4CH2Cl2). In [(Ph3PAu)3Re(CO)4] the metal atoms are arranged in form of a lozenge while in [(Ph3PAu)6AuRe2(CO)8]+ two Au4Re trigonal bipyramids are connected by a common axial Au atom.The treatment of [(Ph3PAu)4Re(CO)4]+ with KOH and Ph3PAuCl in methanol yields the cluster cation [(Ph3PAu)6Re(CO)3]+, which crystallizes with from CH2Cl2 as [(Ph3PAu)6Re(CO)3]PF6 · CH2Cl2 (4 · CH2Cl2). The metal atoms in this cluster form a pentagonal bipyramid with the Re atom in the axial position.  相似文献   

12.
Reaction of (PhMe2P)2PtMe2 or [(κ2-P,N)-Ph2PC2H4NMe2]PtMe2 with an excess of H2SnBu2 or H2SnPh2 resulted in the catalytic formation of cyclo-, oligo- and/or polystannanes. In the reaction of (PhMe2P)2PtMe2 with H2SnBu2, linear oligomeric species H(SnBu2)nH were observed in the initial stage of the reaction, which eventually converted into cyclostannanes. Only polystannanes were observed in the reaction of [(κ2-P,N)-Ph2PC2H4NMe2]PtMe2 with H2SnBu2. The reactions of H2SnPh2 were similar, but more difficult to analyze due to redistribution reactions and the formation of insoluble products. The mechanism of the reactions is clearly different to that previously observed for HSnR3 because metal complexes indicative of oxidative addition/reductive elimination reactions were only observed as minor products.  相似文献   

13.
Infrared, far-infrared and Raman spectra of Re2(O2CCH3)4X2 (X = Cl, Br) and Re2(O2CCD3)4Cl2 have been recorded. Assignments of the vibrational spectra of Os2(O2CCH3)4Cl2 and its deuterated derivative have been completed together with the Re complexes on the basis of normal-coordinate analysis. Force constant calculation was made for the acetate ion as well as for a four-atomic unit (with the CH3 and CD3 groups considered as point masses) using optimized masses of 16.7, 17.8, 20.5 and 21.6 for 12CH3, 13CH3, 12CD3 and 13CD3 groups, respectively. The force constants of the acetate ion have been adopted to the starting force field of the M2(O2CCH3)4X2 type complexes. The metal-halide (0.889, 0.997 and 1.286 N cm−1) and metal-metal stretching (3.32, 3.34 and 3.57 N cm−1) force constants were obtained for Re2(O2CCH3)4Cl2Re2(O2CCH3)4Br2 and Os2(O2CCH3)4Cl2 complexes, respectively. It was shown that the so-called diatomic approximation in most cases overestimates the M-M stretching force constants by 30-40%. Much better correlation has been obtained to fit these force constants, which produced values very close to those obtained by full normal-coordinate calculations. The Re-Re stretching force constants showed a reasonable correlation with the Re-Re bond distances for 18 rhenium complexes.  相似文献   

14.
Reaction of [Mo2O2(μ-S)2(H2O)6]2+ with Mo(CO)6 or metallic Mo under hydrothermal conditions (140 °C, 4 M HCl) gives oxido-sulfido cluster aqua complex [Mo33-S)(μ-O)2(μ-S)(H2O)9]4+ (1). Similarly, [W33-S)(μ-O)2(μ-S)(H2O)9]4+ (2) is obtained from [W2O2(μ-S)2(H2O)6]2+ and W(CO)6. While reaction of [Mo2O2(μ-S)2(H2O)6]2+ with W(CO)6 mainly proceeds as simple reduction to give 1, [W2O2(μ-S)2(H2O)6]2+ with Mo(CO)6 produces new mixed-metal cluster [W2Mo(μ3-S)(μ-O)2(μ-S)(H2O)9]4+ (3) as main product. From solutions of 1 in HCl supramolecular adduct with cucurbit[6]uril (CB[6]) {[Mo3O2S2(H2O)6Cl3]2CB[6]}Cl2⋅18H2O (4) was isolated and structurally characterized. The aqua complexes were converted into acetylacetonates [M3O2S2(acac)3(py)3]PF6 (M3 = Mo3, W3, W2Mo; 5a-c), which were characterized by X-ray single crystal analysis, electrospray ionization mass spectrometry and 1H NMR spectroscopy. Crystal structure of (H5O2)(Me4N)4[W33-S)(μ2-S)(μ2-O)2(NCS)9] (6), obtained from 2, is also reported.  相似文献   

15.
The reaction between CuX2 (X=ClO4, NO3, Cl, Br and CH3COO) and excess of tris(pyrazol-1-yl)methane ligands L (L=CH(pz)3, CH(4-Mepz)3, CH(3,5-Me2pz)3, CH(3,4,5-Me3pz)3 or CH(3-Mepz)2(5-Mepz)) yields [CuX2(L)], [{CuX2}3(L2)2] or [Cu(L2)]X2-type complexes. The ligand to metal ratio is dependent on the number and disposition of the Me substituents on the azole-type ligand and mainly on the nature of the counter-ion X. All complexes have been characterized in the solid state as well as in solution (IR and UV spectra, and conductivity determinations). The solid-state structures of [Cu{(3,5-Me2pz)3CH}2](NO3)2, [Cu{(3,5-Me2pz)3CH}2](ClO4)2·0.5H2O, [Cu{(3,4,5-Me3pz)3CH}2](NO3)2·H2O, [Cu{(4-Mepz)3CH}2]Br2·3H2O have been determined by single crystal X-ray studies.  相似文献   

16.
A novel organic-inorganic hybrid pentaborate [Ni(C4H10N2)(C2H8N2)2][B5O6(OH)4]2 has been synthesized by hydrothermal reaction and characterized by FT-IR, Raman spectroscopy, elemental analyses and DTA-TGA. Its crystal structure was determined from single crystal X-ray diffraction. The structure consists of isolated polyborate anion [B5O6(OH)4] and nickel complex cation of [Ni(C4H10N2)(C2H8N2)2]2+, in which the two kinds of ligands come from the decomposition of triethylenetriamine material. The [B5O6(OH)4] units are connected to one another through hydrogen bonds, forming a three-dimensional framework with large channel along the a and c axes, in which the templating [Ni(C4H10N2)(C2H8N2)2]2+ cations are located. The assignments of the record FT-IR absorption frequencies and Raman shifts were given.  相似文献   

17.
The metalloligand [Pt2(μ-S)2(PPh3)4] reacts with Bi(S2CNEt2)3 or Bi(S2COEt)3 in methanol to produce the orange cationic adducts [Pt2(μ-S)2(PPh3)4Bi(S2CNEt2)2]+ and [Pt2(μ-S)2(PPh3)4Bi(S2COEt)2]+, respectively, isolated as their hexafluorophosphate salts. An X-ray structure determination on [Pt2(μ-S)2(PPh3)4Bi(S2CNEt2)2]PF6 reveals the presence of a six-coordinated bismuth centre with an approximately nido-pentagonal bipyramidal coordination geometry. Fragmentation pathways for both complexes have been probed using electrospray ionisation mass spectrometry; ions [Pt2(μ-S)2(PPh3)2Bi(S2CXEtn)2]+ (X = O, n = 1, X = N, n = 2) are formed by selective loss of two PPh3 ligands, and at higher cone voltages the species [(Ph3P)PtS2Bi]+ is observed. Ions formed by loss of CS2 are also observed for the xanthate but not the dithiocarbamate ions.  相似文献   

18.
Three mono- and dinuclear nickel complexes with dichalcogenolate o-carboranyl ligands were synthesized and characterized by X-ray crystallography. The reactions of Ni(COD)2(COD=1,5-octadiene) with [(THF)3LiE2C2B10H10Li(THF)]2 (E=S, Se) in THF in the presence of air in different ratios afforded the mono- and dinuclear nickel complexes of formulae Li(THF)4]2[Ni(E2C2B10H10)2] (E=S, 1a; E=Se, 1b) and [Li(THF)4]2[Ni2(E2C2B10H10)3] (E=S, 2a; E=Se, 2b). In 2a, two nickel atoms are connected by one chalcogen (η12-S2C2B10H10) bridging ligand with strong metal-metal interaction. Complex of formula (PPh3)2Ni(S2C2B10H10) · 0.5THF (3a) was also obtained from the reaction of (PPh3)2NiCl2 and [(THF)3LiS2C2B10H10Li(THF)]2.  相似文献   

19.
《Inorganica chimica acta》2004,357(2):571-580
Treatment of the ligand N-(2-mercaptoethyl)-3,5-dimethylpyrazole with [Pd(CH3COO)2]3 and reaction of [PdCl(μ-med)]2 with pyridine (py) or triphenylphosphine (PPh3) in the presence of AgBF4 produced the following complexes: [Pd(CH3COO)(μ-med)]2, [Pd(μ-med)(py)]2(BF4)2 and [Pd(μ-med)(PPh3)]2(BF4)2. Similar reactions carried out with 2,2-bipyridine (bpy) or 1,3-bis(diphenylphosphino)propane (dppp) produced [Pd(μ-med)(bpy)]x(BF4)x (x=1 or 2) and [Pd(μ-med)(dppp)]x(BF4)x (x=1 or 2). Treatment of [Pd(μ-med)(bpy)]x(BF4)x with [PdCl2(CH3CN)2] produced [Pd3Cl2(μ-med)2(bpy)2](BF4)2. Treatment of [Pd(μ-med)(dppp)]x(BF4)x with [PdCl2(CH3CN)2] produced a mixture of [Pd(μ-Cl)(dppp)]2(BF4)2 and [Pd(μ-med)2(dppp)]2+. X-ray crystal structures of [Pd(μ-med)(PPh3)]2(BF4)2 · 2CH3CN and [Pd(μ-med)(bpy)]2(BF4)2 · 0.5CH3OH are presented.  相似文献   

20.
The oxidation of Ni(PPh3)4 with BF3 · OEt2, H3CCOOH, and F3CCOOH, and that of (PPh3)2Ni(C2H4) with BF3 · OEt2 is studied by EPR spectroscopy. The reaction of the Ni(0) complexes with BF3 · OEt2 gives Ni(II) complexes with which they react to form Ni(I) compounds with covalent Ni-F and Ni-B bonds that transform with excess BF3 · OEt2 into cationic paramagnetic Ni(I) complexes. Acetic acid also adds oxidatively to Ni(PPh3)4 to form a Ni(II) complex that reacts further to give Ni(I) hydride and carboxylate complexes. The Ni(I) hydride is transformed by the acid into the Ni(I) carboxylate with release of hydrogen, the amount of which depends on the rate of acid addition. The following Ni(I) complexes are identified in the reaction medium: [Ni(PPh3)3]BF4, [(PPh3)2Ni(OEt2)]BF4, [(PPh3)Ni(OEt2)n]BF4, (PPh3)2NiBF2, (PPh3)3NiOOCCH3, and [(PPh3)2Ni(OEt2)P(OEt)3]BF4. Oxidation schemes of Ni(0) complexes by Lewis and Brønsted acids are given.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号