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1.
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
2.
Cobaltacyclopentadiene complexes, (η5-C5H5)(PPh3)(R1) (R1, R2 =; Ph, Me, CO2Me), reacted with RH (RH: triethylsilane, thiocresol, dimethyl- and ethylene-thiourea, pyrrole, thiophene) to give diene complexes, (η5-C5H5)(η4-HCR1CR2CR2CR1R)Co, or uncomplexed, highly substituted butadiene derivatives, HCR1CR2CR2CR1R. The reaction with thiourea proceeded catalytically in the presence of excess of diphenylacetylene although turn-over of the catalyst was small. 相似文献
3.
《Journal of organometallic chemistry》1986,312(3):277-282
Addition at low temperatures of carbon disulfide to a solution of the lithium compound (R1 = CH3, C3H7, Ph, OCH3, SCH3) results in the initial formation of an allenic carbodithioate H2CCC(R1)CSSLi, while for R1 = t-C4H9 or SiMe3 acetylenic carbodithioates R1CCCH2CSSLi are formed. The initial products undergo very rapid subsequent reactions. For R1 = CH3 or C3H7 the lithium compound adds (in the allenic form) in a conjugated fashion to the CCCS system of the allenic carbodithioate. The acetylenic dithioates are deprotonated to give the geminal dithiolates R1CCCHC(SLi)2. For R1 = Ph, OCH3 or SCH3, subsequent deprotonation at the terminal carbon atom of the initial allenic dithioate gives enyne dithiolates HCCC(R1)C(SCH3)2; this reaction proceeds more satisfactorily with the potassium compounds. 相似文献
4.
M(CO)5X (M = Mn, Re; X = Cl, Br, I) reacts with DAB (1,4-diazabutadiene = R1N=C(R2)C(R2)′=NR′1) to give M(CO)3X(DAB). The 1H, 13C NMR and IR spectra indicate that the facial isomer is formed exclusively. A comparison of the 13C NMR spectra of M(CO)3X(DAB) (M = Mn, Re; X = Cl, Br, I; DAB = glyoxalbis-t-butylimine, glyoxyalbisisopropylimine) and the related M(CO)4DAB complexes (M = Cr, Mo, W) with Fe(CO)3DAB complexes shows that the charge density on the ligands is comparable in both types of d6 metal complexes but is slightly different in the Fe-d8 complexes. The effect of the DAB substituents on the carbonyl stretching frequencies is in agreement with the A′(cis) > A″ (cis) > A′(trans) band ordering.Mn(CO)3Cl(t-BuNCHCHNt-Bu) reacts with AgBF4 under a CO atmosphere yielding [Mn(CO)4(t-BuNCHCHN-t-Bu)]BF4. The cationic complex is isoelectronic with M(CO)4(t-BuNCHCHNt-Bu) (M = Cr, Mo, W). 相似文献
5.
Wolfgang A. Herrmann Cornelia Weber Manfred L. Ziegler Orhan Serhadli 《Journal of organometallic chemistry》1985,297(2):245-254
The diazoolefines of composition N2CCR2 (R/R = CH3/CH3 and(-CH2-)5) are suitable precursors of the corresponding vinylidene ligands CCR2. Thus, treatment of the RhRh complex [(η5-C5Me5)Rh(μ-CO)]2 (1) with the N-nitrosourethanes 2a and 2b, resp., in the presence of lithium t-butoxide yields the otherwise inaccessible μ-vinylidene complexes (μ-CCR2)[(η5-C5Me5)Rh(CO)]2 (R = CH3 (3a), R,R = (-CH2-)5 (3b)). The analogous cobalt compound (μ-CCMe2)[(η5-C5Me5)Co(CO)]2 (5a) is obtained similarly. This procedure extends the well-documented diazoalkane method for the synthesis of μ-alkylidene complexes to the less stable diazoalkenes. A single-crystal X-ray diffraction study of the dimethylvinylidene derivative 3a shows the CMe2 ligand to adopt an almost symmetrically metal-bridging position (d(RhC) 197.8(1) and 204.3(1) pm), with a rhodium-rhodium single bond completing a three-membered Rh2C-metallacycle (d(RhRh) 268.4(0) pm) analogous with cyclopropane. 相似文献
6.
2-(MeR1CCR2)-and 2-(CH2CR1CH2CH2)-pyridine (R1,R2 = H or Me) undergo 1,2-double-bond shifts and 2-(CH2CHCH2CH2CH2)-pyridine undergoes a 1,3-double-bond shift on displacement of norbornadiene from [M(CO)4norb] (M = Cr, Mo or W) to give complexes of the type [M(CO)4LL'] (LL' = 2-(allyl)or 2-(substituted allyl)-pyridine), which do not exhibit conformational isomerism involving the plane of the coordinated olefin. 相似文献
7.
Michel Giffard Jack Cousseau Lucien Gouin Marie Renée^Crahe 《Journal of organometallic chemistry》1985,287(3):287-303
In the presence of (SCN)? mercuric chloride HgCl2 adds to acetylenic compounds R1CCR2 affording in most cases α-chloromercuri-β-thiocyanatoalkenes R1C(SCN)C(R2)HgCl and if R1 = R2 = Et or n-Bu isothiocyanates R1C(NCS)C(R2)HgCl. The action of halogens or thio compounds affords α-halo-β-thiocyanatoalkenes. Most of the reported reactions are regio- and stereo-specific, in particular both RC(SCN)CHBr and RCBrCHSCN may be regiospecifically obtained from 1-alkynes RCCH. The synthesis of 1-thiocyanato-1-alkynes is also reported. 相似文献
8.
The effect of the size and branching of alkyl substituents R1 and R2 on the formation of all possible stereoisomers of bis(β-acylvinyl)amines, [R1COCR2CH]2NH, has been investigated. IR and NMR data show that steric requirements of these substituents and resonance stabilization of the s-trans system are the main factors determining the position of the dynamic equilibrium. 相似文献
9.
《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
10.
《Journal of organometallic chemistry》1986,302(2):235-242
Cp(OC)2Mn(THF) reacts with p-diethynylbenzene (Deb), yielding Cp(OC)2Mn(Deb) (I) and [Cp(OC)2Mn]2(Deb) (II) with the η2-acetylene coordination of Deb (to both Mn atoms in II). Under the action of PhLi, I and II are isomerized into Cp(OC)2MnCCHC6H4CCH (III) and [Cp(OC)2MnCCH]2C6H4 (VI). Treatment of I with PhLi, LiBr and an excess of HCl in ether, as well as direct interaction of III with LiBr and HCl/Et2O, gives Cp(OC)2MnCCHC6H4CBrCH2 (IV), which has been characterized by an X-ray single-crystal diffraction study. III adds PPh3, yielding a zwitterionic complex, Cp(OC)2Mn−C(P+Ph3)CHC6H4CCH (V). 相似文献
11.
The successive reaction of (CO)6M with Na[NCR21] and [Et3O]BF4 yields (CO)5M[C(NCR21)OEt] (II: M = Cr; III: M = W; CR21 = C(C6H4Br-p)2 (a), CPh2 (b), C(C6H4OMe-p)2 (c), C(C6H4)2O (d), CBu2tt (e)). Hexacarbonyltungsten, (CO)6W, reacts with Na[NCPh2] and MeOSO2F to give (CO)5W[C(NCPh2) OMe] (IV). X-Ray analysis of IIe shows that: (1) the CNC fragment is almost linear (171.7°); (2) the two NC bond lengths are equal within experimental error; and (3) the O,C,Cr,N plane is perpendicular to the C(Me3),C,N,C(Me3) plane (90.0°). Therefore compounds II–IV are best described as 1-alkoxy-2-azaallenyl complexes. 相似文献
12.
Treatment of perfluoro-n-octanonitrile with phenylphosphine gave tetraphenyltetraphosphine and a spectrum of reduction and interaction products. Fifteen compounds were identified. The imine, (RfC7F15) RfCHNH, and the amine, RfCH2NH2, were the primary reduction products. Secondary phosphorus-free products, some formed following ammonia evolution, were the following: RfCHNCH2Rf, RfCH2CH(NH2)Rf, RfC(NH)NCRf(NH2), RfCH2NHCRf(NH), (RfCN)3, RfCHNCRfNCRf(NH), RfCH2NCRfNHCH2Rf, and RfCH2NCRfNHCRf(NH). Only three phosphorus-containing materials were definitely identified: RfCH(NH2)P(C6H5)H, RfCH[P(C6H5)H]NCHRf, and RfC(NH)P(C6H5)CRf(NH). Depending on reaction conditions, specific phosphorus-containing compounds could be preferentially produced. All the structure assignments are based solely on mass spectral breakdown patterns, since pure compounds were not isolated. 相似文献
13.
J. Levisalles F. Rose-Munch H. Rudler J.C. Daran Y. Jeannin 《Journal of organometallic chemistry》1985,279(3):413-417
The diphosphinoalkyne Ph2PCCPPh2 (2) reacts with the μ-alkylidene complex (CO)9W2[CHCHC(CH3)2] (1) to give, upon insertion of the alkyne into one of the CW bonds of the bridging carbene followed by rupture of a CP bond, a phosphido complex (CO)8W2[C(PPh2)CCHCHC(CH3)2] PPh2 (3). An unexpected long-range 1H31P coupling, through five bonds, is observed in complex 3. 相似文献
14.
The electronegative ligand OTeF5 has been tested on the elements Ti, Mo, W, Ta, Re, Os and others. Compounds such as OMo(OTeF5)4, W(OTeF5)6, Ta(OTeF5)5, ReO2(OTeF5)3, OsO(OTeF5)4 are prepared. While ReVII could be stabilized with OTeF5, the highest oxidation state on Osmium is VI, and Iridium probably IV. OMo(OTeF5)4 shows a regular square pyramidal structure with apical double bonded oxygen. Chemistry on the ligand NTeF5 is based on the synthesis of H2NTeF5 and R3SiNHTeF51. Other new main group derivatives are so far Cl2NTeF5, HClNTeF5, OCN-TeF5, F3PNTeF5, Cl3NPTeF5, F2SNTeF5 and Cl2SeNTeF5, the first compound with a selenium-nitrogen double bond. In the transition metal series the compounds F4MoNTeF5 and Cl4WNTeF5 (in addition to the longer known polymeric (HgNTeF51) have been prepared. Both have discrete metal nitrogen double bonds. 相似文献
15.
One-electron oxidation and one-electron reduction of the electron-rich acetylene derivative, hexakis(trimethylsilyl)-2-butyne [H3C3)3Si]3CCCC[Si(CH3)3]3, unexpectedly produce the persistent radical cation and radical anion of the hitherto unknown neutral compound, tetrakis(trimethylsilyl)butatriene (R3Si)2CCCC(SiR3)2. The radical anion can also be generated from the corresponding diacetylene, bis(trimethylsilyl)-1,3-butadiyne R3SiCCCCSiR3 and potassium metal, obviously via disproportionation. Photoelectron and electron spin resonance spectroscopic data permit the detection and characterization of the individual species. The stability of both the radical anion and the radical cation of the same molecule can be rationalized by the unique combination of the twofold butatriene π-system with 4 R3Si substituents, which can act either as electron donors or electron acceptors and thus stabilize the ground state of either the cation or the anion. 相似文献
16.
Se-Phenyl p-tolueneselenosulfonate (1a) undergoes highly regioselective, photoinitiated, free-radical addition to allenes (R1CHCCR2R3) to afford the regioisomer R1CH(SePh)C(SO2Ar)CR2R3 (13) arising from addition of the p-tolylsulfonyl group to the central carbon of the allene and transfer of the phenylseleno group to the less highly substituted of the two terminal carbons. This regioselectivity, which contrasts with that observed in the majority of radical additions to allenes, can be explained by reference to concepts proposed by Heiba as being important in determining the orientation in different radical additions to allenes. Oxidation of the PhSe group in 13 to PhSe(O) gives allylic selenoxides that undergo a reaction sequence of facile, concerted, [2,3]-sigmatropic rearrangement followed by hydrolysis of the resulting selenenate to afford β-tolylsulfonyl-substituted allylic alcohols, R1CHC(SO2Ar)C(OH)R2R3 (14) in 70–98% yield. Photoaddition of 1a to allenes, followed by the conversion of 13 to 14 thus provides a simple, high-yield route to a wide variety of 14, a class of compounds that would seem to have a number of interesting possible uses in synthesis. 相似文献
17.
RFCCMgX reacts with Ac2O to give not only MeC(O)CCRF but also MeC(O)CXC(RF)C(O)Me, and with CF3COOPr it gives CF3C(O)CHC(OPr)RF not CF3C(O)CCRF; RFCCMgBr reacts with Cl2 to give RFCCBr rather than RFCCCl, while with Br2 RFCCMgI similarly gives RFCCI rather than RFCCBr. 相似文献
18.
The diazo olefins N2CCR2 (R/R = CH3/CH3 and (CH2)5, respectively), generated in situ from the corresponding cyclic N-nitrosourethanes 2a, 2b, are suitable precursors for the corresponding vinylidene ligands 6CCR2. Thus, treatment of the RhRh complex [(η5-C5Me5)Rh(μ-CO)]2 (1) with 2a, 2b in the presence of lithium ethoxide yields the otherwise inaccessible μ-vinylidene complexes (μ-CCR2)[(η5-C5Me5)Rh(CO)]2 (3a, 3b). This procedure extends the well-documented diazoalkane method for synthesis of μ-alkylidene complexes to the less stable diazoalkenes* 相似文献
19.
Experimental data on conformational energies of the molecules FH2CHCCH2, FH2CFCCH2, FH2C(CH3)C&.dbnd;CH2 trans-FH2CHCC(CH3)H have been used to establish parameter values for the nonbonding atom ⋯ atom interaction F ⋯ C(sp2) within the Morse potential formulation. Torsional potentials have been calculated for the four molecules mentioned above and in addition for cis- and trans-FH2CHCCHF, (FH2C)2CCH2, cis-FH2CHCCHCH2F, CH3FCHHCCH2 and FH2CCH2HCCH2. Calculated results have been compared with experimental values. Torsional force constants for the molecules have been obtained. A comparison between fluoro, chloro and bromo compounds is presented. 相似文献
20.
Reaction of nucleophiles with enyne triflates R1R2CC(OTf)CCR31, via an SN-2′ process, results in functionalized enynes by way a 1,3-hydride shift from the initially formed butatrienes. 相似文献