共查询到20条相似文献,搜索用时 31 毫秒
1.
[Pt(C2O4)(dppe)] reacts thermally with PhCCH to produce [Pt(CCPh)2(dppe)], which has been prepared by alternative routes. Similar treatment of [Pt(C2O4)(dppm)] initially produces [Pt(CCPh)2(dppm)], which rearranges to give cis,cis-[Pt2(CCPh)4(μ-dppm)2]. Reaction of [PtCl2(dppm)] with PhCCH/KOH/18-crown-6, or with (PhCC)SnMe3, gives [Pt(CCPh)2(dppm)], which may be converted to the cis,cis-dimer by addition of oxalic acid. Ultraviolet irradiation or refluxing with a trace amount of dppm converts [Pt(CCPh)2(dppm)] to trans,trans-[Pt2(CCPh)4(μ-dppm)2], but the cis,cis-dimer is stable under these conditions. [Pt(C2O4)L2] (L = PPh3, PEt3) complexes also react thermally with PhCCH to yield [Pt(CCPh)2L2] species. 相似文献
2.
The complex [Ir(σ-carb)(CO)(PhCN)(PPh3)], where carb = -7-C6H5-1,2C2B10H10, was found to be an effective catalyst for homogeneous hydrogenation of terminal olefins and acetylenes at room temperature and atmospheric or subatmospheric hydrogen pressure. Internal olefins are not hydrogenated, but simple alk-1-enes are readily converted into the corresponding alkanes. Isomerization of the double bond catalyzed by the metal complex occurs at very small extent. Catalytic hydrogenation of olefins having carboxylate substituents on the unsaturated carbon atoms is prevented by the formation of thermally stable chelate hydridoalkyl complexes of the type I(σ-CHRCHR′C(O)OR″) (σ-carb)(CO)(PPh3)]. Acetylenes are hydrogenated to alkenes. The alk-1-enes formed in the hydrogenation of the alkynes HCCR in turn undergo the more slow reactions either of hydrogenation to alkanes or isomerization to internal olefins which cannot be further hydrogenated. Hydrogenation of alkynes of the type RCCR′ is stereospecifically cis, yielding cis- olefins. Catalyzed cis → trans isomerization reaction of these internal olefins occurs only to a negligeable extent. 相似文献
3.
[WBr2(CO4]n reacts with alkynes to give complexes [WBr2CO(RCCR)2]2 (1) (R = R′ = Me, Et, Ph; R = Me, R′ = Ph), which react with nucleophiles L{L = CNBut, PPh3, or P(OMe)3} to give monoalkyne derivatives (WBr2(CO)(RCCR′)L2](2). An intermediate bis-alkyne adduct [WBr2CO(MeCCMe)2(CNBut)] (3) was isolated in the reaction of [WBr2CO(MeCCMe)2]2 with CNBut illustrating that cleavage of the dimer (1) is the first stage in these reactions. 相似文献
4.
Reduction of various pentafluorophenylnickel(II) complexes in the presence of phosphines gives unstable nickel(I) compounds but Ni(C6F5)(CO)2(PPh3)2 is isolated in the presence of CO. Similar NiR(CO)2(PPh3)2 (R = C6F5,C6Cl5, 2,3,5,6-C6Cl4H) are obtained by reaction of the halogenonickel(I) complex with MgRBr or LiR. Reduction of NiX2L2 in the presence of acetylenes gives [NiXL2]2(μ-PhCCR) (R = H, X = Cl and R = Ph, X = Cl, Br) when L = P-n-Bu3 but only NiX(PPh3)3 are recovered when L = PPh3. No reaction with the alkyne is observed for [NiX(PPh3)2]n but [NiCl(PPh3)]n reacts with RCCR′ to give paramagnetic NiCl(PPh3)(CRCR′) (R = Ph, R′= H, COOEt), diamagnetic [NiCl(PPh3)]2(μ-PhCCPh) and cyclotrimerization when R = R′ = COOMe. Chemical and structural behaviour of the new nickel(I) complexes is described. 相似文献
5.
Reaction of the complexes Ru(CO)2Cl2L [L = 2,2′-bipyridyl (bpy) or 1,10-phenanthroline (phen)] with trifluoromethanesulphonic acid under carefully controlled conditions yields Ru[cis-(CO)2] [cis-(O3SCF3)2] (bidentate complexes. From reactions of the trifluoromethanesulphonates with the appropriate bidentate ligands, the new complexes [cis-Ru(CO)2-L(L′)]2+ (L as above; L′ = 4,4′-dimethyl-2,2′-bipyridyl or 4,4′-diisopropyl-2,2′-bipyridyl) as well as the known [cis-Ru(CO)2L2]2+ and [cis-Ru(CO)2bpy(phen)]2+ have been prepared. 相似文献
6.
《Journal of organometallic chemistry》1988,346(3):C53-C57
The 16-electron fragment (NP3)Rh+ inserts in a highly stereospecific manner across CH bonds from acetylene and 1-alkynes to give the octahedral cis-(alkynyl)hydrides [(NP3)Rh(H)(CCR)]BPh4 (R = H, Ph, COOEt). The structure of the cis-(ethynyl)hydride [(NP3)Rh(H)(CCH)]BPh4 · 1.5 THF has been established by X-ray diffraction. The trigonal bipyramidal rhodium(I) complex [(NP3)RhH], reacts with terminal alkynes to give H2 and the neutral σ-acetylides [(NP3)Rh(CCR)] (R = Ph, COOEt). These undergo metathesis between terminal alkynes and the σ-acetylide ligand through a mechanism involving consecutive breaking and making of CH bonds. 相似文献
7.
《Journal of organometallic chemistry》1986,307(2):237-253
The clusters (μ3-RP)2Fe3(CO09 (1) photochemically add alkines R′CCR′ across their bridging phosphorus centers to yield (μ3-η4-RPCR′CR′PR)Fe3(CO)9 (2). Thermal activation of 2 opens two different reaction channels: Complezes 2 may split into R′CCR′ and 1 in a thermally induced reversion of their photoinitiated formation reaction: in another pathway they may lose Fe(CO)3 to yield (μ2-η2-(PFe)RPCR′CR′PR)Fe2(CO)6 (3). Complex 3 is an Fe2(CO)6 derivative of the butterfly type with the μ2-bridging phosphorus centers linked by an R′CCR′ moeity. The reverse transformation 3 → 2 is induced by Fe2(CO)9 as an “Fe(CO)3” source.Compounds 2 undergo a CO substitution reaction with R′CCR′ to give (μ3-η2- RPCR′CR′PR)(μ3-η2-R′CCR′)Fe3(CO)7 (4) which, upon heating, also transforms into 3. The above reactions 1 ⇋ 2 ⇋ 3 and 2 → 4 → 3 ⇋ 2 present a rare example of a complete closed set of cluster transformations. An analogous subset of reactions is also verified for the arsenic homologues 1, 2 and 4. 相似文献
8.
《Journal of organometallic chemistry》1987,331(1):63-72
Bis(η-cyclopentadienyl)hydridorhenium Cp2ReH undergoes stereospecific trans insertion reactions when treated with monosubstituted acetylenes HCCR (R CO2Me, CN, CF3). The cis alkenyl complexes Cp2Re[η1-(Z)-CHCHR] thus formed isomerize thermally or under acid catalysis to produce the trans isomers Cp2Re[η1-(E)-CHCHR]. When Cp2ReH adds to HCCCOMe only the trans isomer is observed. The regiospecific β-addition of Cp2ReH contrasts with the α-addition of Cp2MoH2 and Cp2WH2. The insertion of acetylenes HCCR′ into the metalcarbon bond of some alkenyl complexes Cp2Re[η1-(E)-CHCHR] affords butadienyl complexes Cp2Re[η1-{(1E,3E)-CHCHR′CHCHR&}] (R,R′ COMe, CO2Me). The (E,E)-configuration of these compounds is deduced from 3J(13-C1H) coupling constants. 相似文献
9.
《Journal of organometallic chemistry》1992,438(3):C15-C22
A large-scale, high-yield synthesis of the aminocarbyne complexes Tp′(CO)2WCN(R)Et (5: R Me; 6: R Et) [Tp′ = hydridotris(3,5-dimethylpyrazol-1-yl)borate] is reported, starting from Tp′W(CO)3I (2). The first step of the synthetic procedure involves thermal decarbonylation of 2 with EtNC to give cis-Tp′W(CO)2(CNEt)I (3). Complex 3 is then reduced with Na/Hg to give the metallate Na[Tp′W(CO)2(CNEt)] (4). Finally, complex 4 is alkylated with RI (R Me, Et) exclusively at the isocyanide nitrogen to give the aminocarbyne complexes 5 and 6. In contrast, the metallates Na[(η5-C5R′5)W(CO)2(CNEt)] (R′ H, Me) undergo alkylation with RI at the metal centre to afford the WII alkyl complexes cis/trans-(η-C5R′5)W(CO)2(CNEt)R. This difference in reactivity is ascribed to the steric demands of the Tp′ ligand, which shields the metal centre from the incoming electrophile. 相似文献
10.
Maxwell A. Cairns Keith R. Dixon Martin A.R. Smith 《Journal of organometallic chemistry》1977,135(1):C33-C34
Syntheses of cis-[PtCl(CH2COCH3)(PEt3)2], cis-[PtCl(CH2NO2) (PEt3)2], and trans-[Pt(CCPh)2 (PEt3)2] are described. The procedure involves reaction of cis-[PtCl2(PEt3)2] with Ag2O and acidic CH bonds to precipitate AgC1 and generate a PtC bond. The method may represent a new general route to platinum—carbon bonds. 相似文献
11.
《Journal of organometallic chemistry》1986,317(2):187-200
The influence of the central metal atom, the trans-X ligand, and the carbyne substituent R on the MCO dissociation step of seventeen different carbyne complexes, trans-(CO)4MCR (X = Cl, Br, I, SePh; M = Cr, W; R = Me, aryl, NEt2), in 1,1,2-trichloroethane was studied by means of the substitution of one CO ligand by PPh3. All complexes react with PPh3 according to the first-order rate equation: — d[complex]/dt = k[complex]. The activation enthalpies ΔH3 are in the range 97–116 kJ mol−1, the activation entropies ΔS3 are 34 to 72 J mol−1 K−1. The reaction rate, (i) is virtually independent of the electronic properties of R, (ii) decreases slightly with increasing steric requirements of R, (iii) increases strongly in the series trans-X = I, Br, Cl, SePh, and (iv) is faster for chromium complexes than for analogous tungsten compounds by a factor of ca. 30 to 50. There is no general correlation between the rate constants k and the CO force constants k(CO). The variation in the reaction rate is essentially determined by the different levels of stabilization of energy in the transition state. The thermolysis of carbyne complexes is also initiated by CO dissociation. The rate of thermolysis when [CO] = 0 is equal to the rate of CO/PPh3 substitution; it decreases rapidly with increasing CO concentration in the solution; and when [CO] = constant it increases significantly with increasing concentration of the complex. A mechanistic scheme is proposed for the thermolysis which involves three different reaction pathways for the coordinatively unsaturated fragment X(CO)3MCR formed by CO dissociation from trans-X(CO)4MCR: readdition of CO, monomolecular decomposition, and reaction with trans-X(CO)4MCR. 相似文献
12.
《Journal of organometallic chemistry》1988,342(2):263-268
Reaction of [PtCl2(cod)] with Ph2PCH2SCH3 yields cis-[PtCl2(Ph2PCH2-SCH3)2] which, on treatment with AgBF4, is converted to [PtC](Ph2PCH2SCH3)2]-BF4, in which one of the ligands is chelated. With [Pt(dba)2], cis-[Pt(Cl2(Ph2PCH2-SCH3)2] reacts to give the platinum(I) complex [Pt2Cl2(μ-Ph2PCH2SCH3)2], which contains a platinum-platinum bond. The terminal chlorides may be replaced by iodide, but the complex is cleaved by carbon monoxide. [Rh2(μ-Cl)2(CO)4] reacts with Ph2PCH2SCH3 to produce [Rh2Cl2(CO)2(μ-Ph2PCH2SCH3)2], whereas with Ph2PCH2CH2SCH3 it yields [RhCl(CO)(Ph2PCH2CH2SCH3)]. A ligand exchange reaction occurs between cis-[PtCl2(Ph2SCH3)2] and [Rh2(μ-Cl)2(CO)4] to give cis-[PtCl2(CO)(Ph2PCH2SCH3)] and [Rh2Cl2(CO)2(μ-Ph2PCH2SCH3)2]. 相似文献
13.
《Journal of organometallic chemistry》1987,323(3):C47-C50
Reaction of RCCH (R Ph, CO2Meor CO2Et) with trans-[M(N2)2(dppe)2] (M Mo or W; dppe Ph2PCH2CH2PPh2) or [Mo(dppm)3] (dppm Ph2PCH2PPh2) gives the alkyne complexes [M(RCCH)2(diphos)2] (diphos dppe, M Mo, R = Ph; dihpos dppm, M Mo, R Ph or CO2Me) and the alkynyl complexes trans-[M(cCR)2(dppe)2], [MH2(CCR)2 (dppe)2] (M Mo or W. R Ph, CO2Me or CO2Et) and cis-[WH(CCCO2Me)(dppe)2]: the X-ray structure of trans-[Mo(CCPh)2(dppe)2] is reported. 相似文献
14.
《Journal of organometallic chemistry》1987,336(3):385-392
Cyclic voltammetric studies on a series of alkynyl complexes [M(CCR)L2(η- C5R′5)] (M = Fe or Ru; R = Ph, Bun or But; L = CO or P-donor ligand; R′ = H or Me) reveal a one-electron oxidation at a glassy carbon electrode in dichloromethane. The chemical reversibility of the oxidation process is dependent upon all four variables (M, L, R and W) considered in this investigation. 相似文献
15.
Pangbu Hong Kenkichi Sonogashira Nobue Hagihara 《Journal of organometallic chemistry》1981,219(3):363-369
Reactions of ketenes (R1R2CCO) with (η5-C5H5)Ni(PPh3)CCR (I) and (η5-C5H5)Fe(CO)(L)CCR (III, L = CO and PPh3) give σ-cyclobut-1-en-3-onyl complexes, {(η5-C5H5)Ni(PPh3)}R1R2 (VI) and (η5-C5H5)Fe(CO)(L)R1R2 (IX)}, (2 + 2) cycloaddition products, in good yields. The σ-cyclobutenonyl complexes also can be prepared by the reaction of I and III with acyl chlorides in the presence of triethylamine. 相似文献
16.
《Journal of organometallic chemistry》1986,312(2):263-276
In order to synthesize penta- and hexa-gonal platinum(II) metallocycles, bidentate ligands such as iminopyridines (L) have been prepared and characterized. The (2-pyridyl)CHNR1 and (2-pyridyl)CH2NCR1R2 ligands react with Zeise's salt to afford directly the pentagonal chelates PtCl2L. Their structure and the cis-stereo-chemistry were shown by the usual spectroscopic methods and for cis-PtCl2[C5H4NCH2NC(CH3)C6H4OH],H2O by an X-ray diffraction study. On the other hand, the (2-pyridyl)(CH2)2NCR1R2 ligands do not afford the expected hexagonal metallocycles; instead, after complexation at the nitrogen atom of the imine they give rise to the (2-pyridyl)ethylamine complex formed after hydrolysis of the coordinated ligands. Complexes trans-[ethylene][(2-pyridyl)(CH2)2NCR1R2]PtCl2 represent when R1 is estradiol a model for “cytotoxic with delayed activity”. 相似文献
17.
The photochemical preparation of [M(CO)5(P(CCC6H5)n(C6H5)3-n], cis-[M(CO)4(PCCC6H5)n(C6H5)3-n] (M = Cr, W; n = 1,2,3) and fac-[Cr(CO)3(P(CCC6H5)(C6H5)3] by the corresponding substitution reactions of the hexacarbonyls is described. The IR and Raman spectra of the complexes in the region of the ν(CO) and ν(CC) vibrations and the 31P NMR spectra are discussed. 相似文献
18.
The chemistry of Cp2V2(CO)5 (I) with alkynes is reported. In non-coordinating solvents, I reacts with large, electron-poor alkynes to give the cyclobutadiene complexes CpV(CO)2(C4R4), which are not formed from photolysis of CpV(CO)4 in the presence of alkyne. Smaller, more basic alkynes give simple monomeric adduct products of the type CpV(CO)2(RCCR). This latter product is the only one obtained if coordinating solvents are employed. It is demonstrated that coupling to form the cyclobutadiene ligand occurs on the dimer. The dimeric intermediate, produced at low temperature and observed at low temperature by IR and NMR, is believed to have the formula Cp2V2(CO)4(μ-RCCR) (X).Cp2V2(CO)5 is active as a catalyst precursor in the photochemical hydrogenation of diphenyl acetylene to cis-stilbene. The mechanism appears to proceed through a Cp2V2(CO)4(alkyne) intermediate. 相似文献
19.
《Journal of organometallic chemistry》1988,339(3):309-321
The reaction of trans-I(CO)4WCNEt2 (I) with a slight excess of PMe3 results in the replacement of one carbonyl group to give mer-I(CO)3(PMe3)WCNEt2 (II). Complex II reacts at room temperature with additional PMe3 under CO replacement to give a mixture of cis- and trans-dicarbonyl-I(CO)2(PMe3)2WCNEt2 (III, IV). Complexes III and IV, which can be separated by column chromatography, isomerize slowly at room temperature, the thermodynamic equilibrium favouring the more stable trans complex IV. The cis isomer III can be obtained from I(CO)2py2WCNEt2 (V) and PMe3. Another CO ligand can be eliminated from III or IV by an excess of PMe3 in boiling hexane and gives mer-I(CO)(PMe3)3WCNEt2 (VI). Moreover complex VI can be prepared by oxidative decarbonylation from III or IV by iodine and subsequent reduction of the intermediate, an isolable, seven-coordinated carbyne complex formulated as (I)3(CO)(PMe3)2WCNEt2 (VII), by two equivalents of PMe3. 相似文献
20.
Lee J. Higham Ann J. Middleton Katie Heslop Paul G. Pringle Angharad Barber A. Guy Orpen 《Journal of organometallic chemistry》2004,689(19):2963-2968
The indan derived diphosphine, cis-1,3-(diphenylphosphino)indan (anphos) is synthesised by the addition of Ph2P(BH3)Li to cis-1,3-dibromoindan followed by deprotection with diethylamine. Anphos readily forms the bicyclic chelates [RhCl(CO)(anphos)], [PtCl2(anphos)], [PtCl(Me)(anphos)] and [FeCl2(anphos)]. The crystal structures of [FeCl2(anphos)] and the monoxide complex, [RhCl(CO)(anphosO)] have been determined. Reaction of the diphosphine with [Rh(acac)(CO)2] under moderate hydroformylation conditions catalysed the formation of 1-heptanal and branched aldehydes from 1-hexene in a ratio of 1.5:1. 相似文献