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 578 毫秒
1.
Cyclic voltammetric studies of clusters (C5H5-C2C6 H4-R-p)Co2(CO)6-n Ln[n=0,2; L=PPh3, P(OEt)3] and (RCH2C)2Co2(CO4) (PPh3)2 on Pt electrode are described. The primary reduction (0 / ?1) and oxidation (+ 1 / 0) steps are considered as a mono-electron process for all clusters. For the clusters (C5H5C2C6H4-R-p)Co2(CO)6, a good linear relation between reduction potential Epred and Hammett constant σp of R in the clusters is found. For the clusters (RC2R')Co2(CO)4L2, their radical anions are extremely unstable at room temperature and fragment into a series of mononuclear species, one of which is (RC2R')Co(CO)2PPh3. The reaction of radical anions of (RC2R')Co2(CO)6–n (PPh3)n(n=0,2) with PPh3 also produces mononuclear species (RC2R')Co(CO)2PPh3 which has been detected by means of cyclic voltammetry and ESR. The influence of R on redox properties of clusters is discussed.  相似文献   

2.
RuHCl(CO)2(PPh3)2 reacts with ethylene under mild conditions (25 psi, 80°C) to yield a propionyl derivative RuCl(C[O]C2H5)(CO)(PPh3)2 which is believed to be coordinatively unsaturated. Unlike the acetyl analogue, RuCl[C[O]C2H5(CO)-(PPh3)2 does not isomerize to RuCl(C2H5)(CO)2(PPh3)2 in solution. Under one atmosphere of carbon monoxide, RuCl(C[O]C2H5(CO)(PPh3)2 exists in equilibrium with two species believed to be RuCl(C[O]C2H5)(CO)2(PPh3)2 and [Ru(C[O]C2H5)(CO)3(PPh3)2]Cl. RuCl(C[O]C2H5)(CO)(PPh3)2 reacts with CO/ AgClO4 to give mer-[Ru(C[O]C2H5)(CO)3(PPh3)2]ClO4, p-tolylisocyanide (RNC) and NaClO4 to give cis-[Ru(C[O]C2H5)(CO)(CNR)2(PPh3)2ClO4, and hydrochloric acid to yield the hydroxycarbene complex, RuCl2(CO)(C[OH]C2H5)(PPh3)2.  相似文献   

3.
Summary Equimolar quantities of [MI2(CO)3(NCMe)2] (M = Mo or W) and C3H4N2 (pyrazole) react in CH2C12 at room temperature to give the iodo-bridged dimers [M(μ-I) (CO)3(C3H4N2)]2 (1) and (2). Two equivalents of C3H4N2 react with [MI2(CO)3(NCMe)2] (M = Mo or W) to give the bis(pyrazole) complexes [MI2(CO)3(C3H4N2)2] (3) and (4) in good yield. Three and four equivalents of pyrazole react with [MoI2(CO)3(NCMe)2] to give the cationic complexes [MoI(CO)3(C3H4N2)3]I (5) and [MoI(CO)2(C3H4N2)4]I (6), respectively. The mixed ligand complexes [MI2(CO)3(C3H4N2)L] (M = Mo or W; L = PPh3, AsPh3 or SbPh3) (7)-(12) are prepared by reacting equimolar amounts of [MI2(CO)3(NCMe)2] and L in CH2C12 at room temperature, followed by an in situ reaction with one equivalent of C3H4N2. The MoSnCl3 complex [MoCl(SnCl3)(CO)3(C3H4N2)2] (13) is prepared in an analogous manner using acetone as the solvent, whilst the mixed ligand compound [MoCl(SnQ3)(CO) 3(C3H4N2)(PPh3)] (14) was prepared by treating the dimeric complex [Mo(μ-Cl)(SnCl3)(CO)3(PPh3)]2 with two equivalents of C3H4N2. All the new complexes were characterised by elemental analysis (carbon, hydrogen and nitrogen), i.r. and 1H n.m.r. spectroscopy.  相似文献   

4.
Conclusions The photochemical reactions of (CO)2(PPh3)MnC5H4Fe(CO)2C5H5 and (CO)2(PPh3)MnC5H4COFe(CO)2C5H5 with PPh3 gave the products of replacing the CO on the Fe atom by PPh3: respectively (CO)2(PPh3)MnC5H4Fe (CO)(PPh3)C5H5 and (CO)2(PPh3)MnC5H4COFe(CO)(PPh3)C5H5.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2813–2815, December, 1977.  相似文献   

5.
Three new heterobimetallic acetylene complexes CpNiCo (CO)3 (PPh3) (PhC2C4H4-R-p) [R = H (2), Br (3), COCH2 (4)] have been synthesized in suitable yield (31–47%) via the reaction of (PhC2C3H4-R-p)CO2(CO)5 PPh2 with nickelcene in n-octane. The complex CpNiCo(CO)3 (Ph2C3) (1) has also been obtained in 12% by the reaction of (Ph2C2) Co2 (CO)4 with nickelcene. The complexes have been characterized by elemental analysis, IR and 1H NMR. Electrochemical study of redox couples of these complexes was presented by using cyclic voltammetry on Pt electrodes in acetone. At room temperature, all complexes underwent electrochemically reversible or guasi-reversible oneelectron oxidation or reduction to the stable radicals. The radical anions of the complexes could be easily detected by ESR method in situ electrolysis in the THF solution. The isotropic parameters, <a>CO=2.20mT, <g> = 2.052 for the radical anion of complex 1, <a>CO= 2.20 mT, <a>P = 1.42 mT, <g>=2.057 for the radical anion of complex 2, might indicate that NiCoC2 framework is a delocalized unit and the ligand obitals in the complex have more contribution to the LUMO of the complex.  相似文献   

6.
Reactions of 2-(diphenylphosphinomethyl)aniline, H2L1, with [MNCl2(PPh3)2] complexes (M = Re, Tc) give the bis-chelates [MNCl(H2L1)2]Cl (M = Re, Tc) or the mono-chelate [ReNCl2(PPh3)(H2L1)] depending on the conditions applied. The aminophosphine reacts as a bidentate, neutral ligand in all three cases. The complexes were studied spectroscopically and by X-ray crystallography.  相似文献   

7.
The reaction of p‐(N,N‐dimethylaminophenyl)diphenylphosphine [PPh2(p‐C6H4NMe2)] with [Fe3(CO)12], [Rh(CO)2Cl]2 and PdCl2 resulted in three new mononuclear complexes, {Fe(CO)4[η1‐(P)‐PPh2(p‐C6H4NMe2)]} ( 1a ), trans‐{Rh(CO)Cl[η1‐(P)‐PPh2(p‐C6H4NMe2)]2} ( 2 ) and trans‐{PdCl2[η1‐(P)‐PPh2(p‐C6H4NMe2)]2} ( 3 ), respectively. A small amount of dinuclear nonmetal‐metal bonded complex, {Fe2(CO)8[µ‐(P,N)‐PPh2(p‐C6H4NMe2)]} ( 1b ), was also isolated as a side product in the reaction of [Fe3(CO)12]. The complexes were characterized by elemental analyses, mass, IR, UV–vis, 1H, 13C (except 1b) and 31P{1H} NMR spectroscopy. The Pd complex 3 effectively catalyzes the Suzuki–Miyaura cross‐coupling reactions of aryl halides with arylboronic acids in water–isopropanol (1:1) at room temperature. Excellent yields (up to 99% isolated yield) were achieved. The effects of different solvents, bases, catalyst quantities were also evaluated. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

8.
The reactivity of [Pt2(μ-S)2(PPh3)4] towards [RuCl2(η6-arene)]2 (arene=C6H6, C6Me6, p-MeC6H4Pri=p-cymene), [OsCl2(η6-p-cymene)]2 and [MCl2(η5-C5Me5)]2 (M=Rh, Ir) have been probed using electrospray ionisation mass spectrometry. In all cases, dicationic products of the type [Pt2(μ-S)2(PPh3)4ML]2+ (L=π-hydrocarbon ligand) are observed, and a number of complexes have been prepared on the synthetic scale, isolated as their BPh4− or PF6− salts, and fully characterised. A single-crystal X-ray structure determination on the Ru p-cymene derivative confirms the presence of a pseudo-five-coordinate Ru centre. This resists addition of small donor ligands such as CO and pyridine. The reaction of [Pt2(μ-S)2(PPh3)4] with RuClCp(PPh3)2 (Cp=η5-C5H5) gives [Pt2(μ-S)2(PPh3)4RuCp]+. In addition, the reaction of [Pt2(μ-S)2(PPh3)4] with the related carbonyl complex [RuCl2(CO)3]2, monitored by electrospray mass spectrometry, gives [Pt2(μ-S)2(PPh3)4Ru(CO)3Cl]+.  相似文献   

9.
Summary The compound [Re(CO)3(PPh3)2Cl] reacts with the lithium salt of thiazole derivatives (L1H = 2-amino-benzothiazole, L2H = 2–N-methyl-aminothiazole, L3H = 2–N-phenylaminothiazole, L4H = 2–N-(4-methoxyphenyl)aminothiazole, L5H = 2–N(4-nitrophenyl)aminothiazole) to give [Re(CO)2-(PPh3)2(L)]. The compounds have been characterized by elemental analysis, i.r. and1H n.m.r. spectra. At room temperature [Re(CO)2(PPh3)(L2)] reacts with L6H (L6H = diphenylacetic acid), to give the carboxylato complex [Re(CO)2 .The crystal structures of [Re(CO)2(PPh3)2(L2)] (2) and [Re(CO)2(PPh3)2(L6)] (6) were determined by x-ray crystallography. [Re(CO)2(PPh3)2(L2)] crystallizes in the monoclinic space group P21/m witha = 9.16(1),b= 24.82(2),c =9.12(1) Å, and = 115.81(4)°; Dc = 1.56 g cm–3for Z = 2.The structure was refined to a final R of 6.4%. The molecules have Cs symmetry. The rhenium atom is six-coordinate with approximately octahedral geometry. The anionic ligand is chelating through the nitrogen atoms and is strictly planar allowing delocalization of the -electron density. [Re(CO)2(PPh3)2(L6)] (6) crystallizes in the monoclinic space group P21/n witha = 22.203(5),b = 18.651(5),c =10.653(3) Å, = 91.08(3)°, Dc = 1.47 g cm–3 for Z = 4. The structure was refined to a final R of 4.7%. The complex is monomeric and the rhenium atom is distorted octahedral with two mutuallytrans PPh3 ligands, twocis CO ligands and one chelating Ph2CHCO 2 – ion.  相似文献   

10.
Several new hexa-coordinated ruthenium(II) and penta-coordinated rhodium(I) complexes of the types [RuCl(CO)(PPh 3 ) 2 (TSC)], [RuH(CO)(PPh 3 ) 2 (TSC)], and [Rh(PPh 3 ) 3 (TSC)] (where TSC = anion of thiosemicarbazone Schiff bases) have been prepared by the reactions of [RuHCl(CO)(PPh 3 ) 3 ], [RuH 2 (CO)(PPh 3 ) 3 )], and [RhH(PPh 3 ) 4 ] with thiosemicarbazones of 2-furaldehyde (H-FTSC), thiophene-2-carboxaldehyde (H-TCTSC), p-anisaldehyde (H-ATSC), piperonaldehyde (H-PTSC), and cyclohexanone (H-CTSC). All the new complexes obtained have been characterized on the basis of elemental analysis, IR, 1 H NMR, 31 P NMR, and electronic spectral data.  相似文献   

11.
The reaction of Ru3(CO)10(dotpm) ( 1 ) [dotpm = (bis(di‐ortho‐tolylphosphanyl)methane)] and one equivalent of L [L = PPh3, P(C6H4Cl‐p)3 and PPh2(C6H4Br‐p)] in refluxing n‐hexane afforded a series of derivatives [Ru3(CO)9(dotpm)L] ( 2 – 4 ), respectively, in ca. 67–70 % yield. Complexes 2 – 4 were characterized by elemental analysis (CHN), IR, 1H NMR, 13C{1H} NMR and 31P{1H} NMR spectroscopy. The molecular structures of 2 , 3 , and 4 were established by single‐crystal X‐ray diffraction. The bidentate dotpm and monodentate phosphine ligands occupy equatorial positions with respect to the Ru triangle. The effect of substitution resulted in significant differences in the Ru–Ru and Ru–P bond lengths.  相似文献   

12.
The o‐substituted hybrid phenylphosphines, PPh2(o‐C6H4NH2) and PPh2(o‐C6H4OH), could be deprotonated with LDA or n‐BuLi to yield PPh2(o‐C6H4NHLi) and PPh2(o‐C6H4OLi), respectively. When added to a solution of (η5‐C5H5)Fe(CO)2I at room temperature, these two lithiated reagents produce a chelated neutral complex 1 (η5‐C5H5)Fe(CO)[C(O)NH(o‐C6H4)PPh2‐C,P‐η2] for the former and mainly a zwitterionic complex 2 , (η5‐C5H5)Fe+(CO)2[PPh2(o‐C6H4O?)] for the latter. Complex 1 could easily be protonated and then decarbonylated to give 4 [(η5‐C5H5)Fe(CO){NH2(o‐C6H4)PPh2‐N,P‐η2}+]. Complexes 1 and 4‐I have been crystallographically characterized with X‐ray diffraction.  相似文献   

13.
The reactions of ruthenium(II) complexes, [RuHCl(CO)(PPh3)2(B)] [B = PPh3, pyridine (py) or piperidine (pip)], with bidentate Schiff base ligands derived by condensing salicylaldehyde with aniline, o-, m- or p-toluidine have been carried out. The products were characterised by analytical, i.r., electronic, 1H-n.m.r. and 31P-n.m.r. spectral studies and are formulated as [RuCl(CO)(L)(PPh3)(B)] (L = Schiff base anion; B = PPh3, py or pip). An octahedral structure has been tentatively proposed for the new complexes. The Schiff bases and the new complexes were tested in vitro to evaluate their activity against the fungus Aspergillus flavus.  相似文献   

14.
Transition Metal Silyl Complexes, 44. — Preparation of the Binuclear Silyl Complexes (CO)3(R3Si)Fe(μ-PR′R′′)Pt(PPh3)2 by Oxidative Addition of (CO)3(R′R′′HP)Fe(H)SiR3 to (C2H4)Pt(PPh3)2 The complexes (CO)3(R′R′′HP)Fe(H)SiR3 ( 1 ) [PHR′R′′ = PHPh2, PH2Ph, PH2Cy; SiR3 = SiPh3, SiPh2Me, SiPhMe2, Si(OMe)3] react with Pt(C2H4)(PPh3)2 to give the dinuclear, silyl-substituted complexes (CO)3(R3Si)Fe(μ-PR′R′′)Pt(PPh3)2 ( 2 ) in high yields. Upon reaction of 2 (R = R′ R′′ = Ph) with CO, the PPh3 ligand at Pt being trans to the PPh2 bridge is exchanged, and (CO)3(Ph3Si)Fe(μ-PPh2)Pt(PPh3)CO ( 3 ) is formed. Complex 3 is characterized by an X-ray structure analysis. The rather short Fe — Si distance [233.9(2) pm] and the infrared spectrum of 3 indicate that the Fe — Pt bond is quite polar.  相似文献   

15.
Protonation of the closely related salts [N(PPh3)2][W(CC6H4Me-4)(CO)2(η-1,2-C2B9H9R2] (Ia, R = H; Ib, R = Me) affords structurally different products: [N(PPh3)2][W2(μ-H){μ-C2(C6H4Me-4)2}(CO)4(η-1,2-C2B9H11)2] (III) and [W(CC6H4Me-4)(CO)2(η-1,2-C2B9H10Me2)] (V), respectively. Treatment of Ib, with PMe3, gives the ketenyl complex [N(PPh3)2][W(CO)(PMe3){η2-C(C6H4Me-4)C(O)}(η-1,2-C2B9H9Me2)] (VI). Protonation and methylation of the latter yields the alkyne-tungsten compounds [W(CO)(PMe3){η-C2(OR′)(C6H4Me-4)}(η-1,2-C2B9H9Me2)] (IXa, R′ = H; IXb, R′ = Me).  相似文献   

16.
Abstract

A series of complexes having the general formula, [Co(CNR)3(PR3)2]X2, X = ClO4, BF4 with CNR = CNCMe3, CNCHMe2, CNC6H11. CNCH2Ph and PR3 = PPh3, P(C6H4Me-p)3, P(C6H4OMe-p)3 has been synthesized and characterized. Synthesis can be achieved by reaction of [Co(CNR)4(AsPh3)2]X2 complexes with controlled excess of PR3 ligands, and by AgClO4/AgBF4 oxidation of the [Co(CNR)3(PR3)2]X complexes. The latter procedure is preferable. Alternate syntheses of the [Co(CNR)3(PR3)2]X complexes have also been employed. Five-coordinate Co(II) complexes have not been obtained using CNCMe3 with P(C6H4Me-p)3 ligands, CNCH2Ph with P(C6H4OMe-p)3 ligands, or CNC4H9-n with PPh3 ligands. [Co(CNC-Me3)3{P(C6H4Cl-p)3}2]ClO4 produced only [Co{CNCMe3)4H2O](ClO4)2 upon forced oxidation with excess AgClO4. [Co(CNR)3(PR3)2]X2 complexes appear to undergo varying degrees of distortion from regular (i.e., D 3h symmetry) axially-disubstituted trigonal bipyramidal coordination in the solid state, as evidenced by v(-N°C) IR patterns, but to assume regular trigonal bipyramidal coordination in solution. Effective magnetic moments indicate one-electron paramagnetism, and solution electronic spectra are compatible with trigonal bipyramidal coordination.  相似文献   

17.
Complexes of general formula [ReOX2{(C5H4N)CH(O)CH2(C5H4N)}] (X?=?Cl,?I) were prepared by reaction of trans-[ReOCl3(PPh3)2] and trans-[ReOI2(OEt)(PPh3)2] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. The coordinated DPE ligand undergoes addition of water at the ethylenic carbon atoms, and the (C5H4N)CH(O)CH2(C5H4N) moiety acts as a uninegative terdentate N,O,N-donor ligand. X-ray crystal structures of both complexes have been determined and show distorted octahedral geometry at the rhenium(V) centre.  相似文献   

18.
The reactions of K[HB(pz)3] (pz = pyrazol-1-yl) with the coordinatively unsaturated σ-vinyl complexes [Ru(CRCHR)Cl(CO)(PPh3)2] (R = H, Me, C6H5) proceed with loss of a chloride and a phosphine ligand to provide the compounds [Ru(CRCHR)(CO)(PPh3){HB(pz)3}] in high yield. Similar treatment of the complex [Ru(C6H4Me-4)Cl(CO)(PPh3)2] leads to the related σ-aryl derivative [Ru(C6H4Me-4)(CO)(PPh3){HB(pz)3}] whilst the complex [RuClH(CO)(PPh3)3] treated successively with diphenylbutadiyne and K[HB(pz)3] provides the unusual derivative [Ru{C(CCPh)CHPh}(CO)(PPh3){HB(pz)3}].  相似文献   

19.
Summary The rhodium(I) carbonyl compounds [Rh(CO)L22] [BF4]. 1/2CH2Clnn2 (L = PPh2 or AsPh3) react with the nucleophiles OMe−, RCOO− (R = Me, Et) under nitrogen to form [Rh(OR)(CO)L2] (1)–(2) and [Rh(OOCR)(CO)L2] (7)–(10), respectively. Addition of [Rh(CO)2(PPh3)2]-[BF 4] to OMe− under nitrogen produces [Rh(COOMe)-(CO) (PPh3)2]-MeOH (3), whilst reactions of [Rh(CO)-(PPh3)2] [BF4]·1/2CH2Cl2 and [Rh(CO)2(PPh3)2] [BF4] with OR- (R = Me, Et or n-Pr) in the presence of CO produce [Rh(COOR)(CO)2(PPh3)2] (4)–(6). The products have been characterised by i.r., 1H, 31P, 13Cn.m.r. spectroscopy and elemental analysis.  相似文献   

20.
Substituted phosphines of the type Ph2PCH(R)PPh2 and their PtII complexes [PtX2{Ph2PCH(R)PPh2}] (R = Me, Ph or SiMe3; X = halide) were prepared. Treatment of [PtCl2(NCBut)2] with Ph2PCH(SiMe3)-PPh2 gave [PtCl2(Ph2PCH2PPh2)], while treatment with Ph2PCH(Ph)PPh2 gave [Pt{Ph2PCH(Ph)PPh2}2]Cl2. Reaction of p-MeC6H4C≡CLi or PhC≡CLi with [PtX2{Ph2PCH(Me)PPh2}] gave [Pt(C≡CC6H4Me-p)2-{Ph2PCH(Me)PPh2}] (X = I) and [Pt{Ph2PC(Me)PPh2}2](X = Cl),while reaction of p-MeC6H4C≡CLi with [Pt{Ph2PCH(Ph)PPh2}2]Cl2 gave [Pt{Ph2PC(Ph)PPh2}2]. The platinum complexes [PtMe2(dpmMe)] or [Pt(CH2)4(dpmMe)] fail to undergo ring-opening on treatment with one equivalent of dpmMe [dpmMe = Ph2PCH(Me)PPh2]. Treatment of [Ir(CO)Cl(PPh3)2] with two equivalents of dpmMe gave [Ir(CO)(dpmMe)2]Cl. The PF6 salt was also prepared. Treatment of [Ir(CO)(dpmMe)2]Cl with [Cu(C≡CPh)2], [AgCl(PPh3)] or [AuCl(PPh3)] failed to give heterobimetallic complexes. Attempts to prepare the dinuclear rhodium complex [Rh2(CO)3(μ-Cl)(dpmMe)2]BPh4 using a procedure similar to that employed for an analogous dpm (dpm = Ph2PCH2PPh2) complex were unsuccessful. Instead, the mononuclear complex [Rh(CO)(dpmMe)2]BPh4 was obtained. The corresponding chloride and PF6 salts were also prepared. Attempts to prepare [Rh(CO)(dpmMe)2]Cl in CHCl3 gave [RhHCl(dpmMe)2]Cl. Recrystallization of [Rh(CO)(dpmMe)2]BPh4 from CHCl3/EtOH gave [RhO2(dpmMe)2]BPh4. Treatment of [Rh(CO)2Cl2]2 with one equivalent of dpmMe per Rh atom gave two compounds, [Rh(CO)(dpmMe)2]Cl and a dinuclear complex that undergoes exchange at room temperature between two formulae: [Rh2(CO)2(μ-Cl)(μ-CO)(dpmMe)2]Cl and [Rh2(CO)2-(μ-Cl)(dpmMe)2]Cl. This revised version was published online in June 2006 with corrections to the Cover Date.  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