共查询到20条相似文献,搜索用时 31 毫秒
1.
Georg Grötsch Wolfgang Malisch Herbert Blau 《Journal of organometallic chemistry》1983,252(2):C19-C22
The reaction of the phosphonium metallates Me4P[C5R5(CO)(Me3P))R′] (M = W, R = H, R′ = Et (1a); M = Mo, R = Me, R′ = Me (1b)) with the silylating reagent Me3SiOSO2CF3 yields the neutral complexes C5R5(CO)(Me3P))R (2a, 2b) bearing a chelating O(2), C(4)-trimethylsiloxybutenone ligand. The structure of the new compounds is established by the IR, 1H and 31P NMR spectra. 相似文献
2.
The tertiary phosphines R2PF2)n (R = C6H5 or C6H11; n = 2,3, or 4) react with M(CO)6 (M = Cr, Mo, W) to give R2PF2)nM(CO)5 in which the ligand is bonded to M through P alone. Similar bonding is found in some chloro-complexes of platinum and palladium. 相似文献
3.
Reaction of the 16 electron monomer [Co(η5-C5H5)(S2C2{CN}2)] with various tertiary phosphines and phosphites (L) gives readily the 18 electron monomers [Co(η5-C5H5)(S2C2{CN}2)L] which for L = P(OR)3 have J(C55) ca. 6 Hz but J(C55) = 0 for L = PR3. 相似文献
4.
G.Michael Bancroft Ian Adams David K. Creber Dean E. Eastman Wolfgang Gudat 《Chemical physics letters》1976,38(1):83-87
High resolution photoelectron spectra of Me2Cd (Me = CH3) in the gas phase, and organotin compounds in the solid state show that the 4d9 final state produced in the photoelectron experiment splits in the presence of ligand fields. Only the C20 crystal field term (the term that transforms like the electric field gradient) contributes to the splitting. The 4d splitting in Me2Cd and trans-Me2Sn(BzBz)2 (BzBz = anion of dibenzoylmethane) are 0.21 ± 0.01 eV and 0.35 ± 0.1 eV respectively. The observed 4d linewidth for Ph4Sn (Ph = C6H5) of 0.67 eV indicates that very narrow linewidths can be obtained on molecular nonconducting solids. The constant spin-orbit splitting values, combined with nuclear field gradients from Mössbauer and NQR measurements, strongly indicate that a previously proposed explanation for the increase in apparent spin-orbit coupling in Cd metal is untenable. 相似文献
5.
Frédéric-Georges Fontaine 《Journal of organometallic chemistry》2006,691(22):4595-4600
Reaction of 2 equiv. of (C4Me4P)Li(tmeda) (tmeda = tetraethylenediamine) with 1 equiv. of ScCl3(THF)3 gave the new compound (η5-C4Me4P)2ScCl2Li(tmeda) (1), which was characterized by X-ray crystallography. A phospholyl moiety in 1 is labile, as demonstrated by reactions of 1 with LiCH(SiMe3)2 and Cp∗Li (Cp∗ = C5Me5) to afford, respectively, (η5-Me4C4P)Sc[CH(SiMe3)2]Cl2Li(tmeda) (4) and (η5-Me4C4P)Cp∗ScCl2Li(tmeda) (5). Attempts to generate alkyl derivatives of the general type (η5-C4Me4P)2ScR (R = alkyl) were unsuccessful. 相似文献
6.
Results of studies of the nucleophilic aroylation of PhCO2Me, Me3CCO2Me and Ph2CO by several low temperature ArLi/CO systems (Ar =C6H5, p-CH3C6H4, -CH3C6H4, 2,6-(CH3)2C6H3 and 2,4,6-(CH3)3C6H2) are reported. The experiments with C6H5Li were unsuccessful and the best results were obtained with 2,6-(CH3)2-C6H3Li. 相似文献
7.
Reaction of chlorodiphenylphosphine with (η5-C5H5)(η7-C7H6Li)Ti gave (η5-C5H5)[η7-C7H6P(C6H5)2]Ti in good yields. This novel phosphinetitanium (II) derivative displaced one carbonyl of metal carbonyl complexes [Ni(CO)4, Fe(CO)5 and Mo(CO)6] to afford heterobimetallic complexes containing low valent titanium, and behaved as a poor electron-donating phosphine. 相似文献
8.
Dr. Takahito Watanabe Yumi Kasai Prof. Dr. Hiromi Tobita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(59):13491-13495
Reaction of N-heterocyclic carbene (NHC)-stabilized PGeP-type germylene Ge{o-(PiPr2)C6H4}2⋅MeIiPr ( 1 ) (MeIiPr=1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) with Ni(cod)2 gave pincer germylene complex Ni[Ge{o-(PiPr2)C6H4}2](MeIiPr) ( 2 ), in which the Ge center of 2 is significantly pyramidalized. Theoretical calculation on 2 predicted the ambiphilicity of the germanium center, which was confirmed by reactivity studies. Thus, complex 2 reacted with both Lewis base MeIMe (MeIMe=1,3,4,5-tetramethylimidazol-2-ylidene) and Lewis acid BH3⋅SMe2 at the germanium center to afford the adducts Ni[Ge{o-(PiPr2)C6H4}2⋅MeIMe](MeIiPr) ( 3 ) and Ni[Ge{o-(PiPr2)C6H4}2⋅BH3](MeIiPr) ( 4 ), respectively. Furthermore, the former was slowly converted to dinuclear complex Ni2[Ge{o-(PiPr2)C6H4}2]2(MeIMe)2 ( 5 ) at room temperature. Complex 5 can be regarded as a dimer of the MeIMe analog of 2 with a Ni-Ge-Ge-Ni linkage. 相似文献
9.
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
10.
Intensively coloured stibinidene complexes (LnM)2SbR (LnM = (CO)5Cr; R = tBu, Cl, I, EtS. LnM = C5H5(CO)2Mn; R = Cl. LnM = CH3C5H4(CO)2Mn; R = Br) which contain trigonally planar coordinated Sb(+1) with the stibanediyl ligand stabilized by M Sb(R) M-π-bonding have been obtained. Their synthesis and properties as well as an X-ray structure determination of [CH3C5H4(CO)2Mn]2SbBr are described. 相似文献
11.
The addition of trimethylphosphane to five-membered metallacyclic vinylketone complexes of the type ArR) (I) (Ar = η5-aromatic ring system: C5H5, C5H4Me, C5Me5; R = Me, Et, n-Bu; M = Mo, W) in pentane solution results in the formation of the ylidic metallacyclopropane complexes ArH(COR)] (II). In these 1:1 adducts the three-membered ring is stabilized by an electron-donating phosphonium and an electron-attracting acyl substituent. The negative charge in the ylidic complexes II is localized on the central metal providing it with Lewis base properties. An extraordinary high electron density can be observed on the metal of the derivative C5H5H-(COMe)] (III) which is formed by a 1:2 addition of C5H5W(CO)(C2H2)-(COMe) and PMe3. The metallacyclopropane complexes II and III are characterized by IR, 1H NMR, 13C NMR, 31P NMR and mass spectroscopy. For C5H5H(COMe)], the results of an X-ray structure determination are presented. 相似文献
12.
Ronald E. Banks Ismail M. Farhat Roy Fields Robin G. Pritchard Mohamad M. Saleh 《Journal of fluorine chemistry》1985,28(3):325-340
The nitrosoarenes ArNO (Ar = C6H5, 2-MeC6H4, 2,4,6- Me3C6H2 and C6F5) have been condensed with 4-(dichloroamino)- tetrafluoropyridine to provide the azoxy-compounds pyFN()Ar (pyF = 2,3,5,6-tetrafluoro-4-pyridyl); de-oxygenation of the first three with triphenylphosphine or triethyl phosphite gave the corresponding azo-compounds, and the reverse reaction was achieved in the case of pyFNNC6H2Me3-2,4,6 using peroxytrifluoroacetic acid. Thermolysis of 4-azidotetrafluoropyridine in the presence of pentafluoronitrosobenzene provided the perfluorinated azoxy-compound pyFN()C6F5. X-Ray methods have been used to determine the molecular geometry of pyFN()C6H2Me3-2,4,6. 相似文献
13.
Luis Werner Julika Hagn Janis Walpuski Prof. Dr. Udo Radius 《Angewandte Chemie (International ed. in English)》2023,62(51):e202312111
The three-coordinate aluminum cations ligated by N-heterocyclic carbenes (NHCs) [(NHC) ⋅ AlMes2]+[B(C6F5)4]− (NHC=IMeMe 4 , IiPrMe 5 , IiPr 6 , Mes=2,4,6-trimethylphenyl) were prepared via hydride abstraction of the alanes (NHC) ⋅ AlHMes2 (NHC=IMeMe 1 , IiPrMe 2 , IiPr 3 ) using [Ph3C]+[B(C6F5)4]− in toluene as hydride acceptor. If this reaction was performed in diethyl ether, the corresponding four-coordinate aluminum etherate cations [(NHC) ⋅ AlMes2(OEt2)]+ [B(C6F5)4]− 7 – 9 (NHC=IMeMe 7 , IiPrMe 8 , IiPr 9 ) were isolated. According to a theoretical and experimental assessment of the Lewis-acidity of the [(IMeMe) ⋅ AlMes2]+ cation is the acidity larger than that of B(C6F5)3 and of similar magnitude as reported for Al(C6F5)3. The reaction of [(IMeMe) ⋅ AlMes2]+[B(C6F5)4]− 4 with the sterically less demanding, basic phosphine PMe3 afforded a mixed NHC/phosphine stabilized cation [(IMeMe) ⋅ AlMes2(PMe3)]+[B(C6F5)4]− 10 . Equimolar mixtures of 4 and the sterically more demanding PCy3 gave a frustrated Lewis-pair (FLP), i.e., [(IMeMe) ⋅ AlMes2]+[B(C6F5)4]−/PCy3 FLP-11 , which reacts with small molecules such as CO2, ethene, and 2-butyne. 相似文献
14.
Dr. Tetsuya Fukuda Dr. Hisako Hashimoto Prof. Dr. Shigeyoshi Sakaki Prof. Dr. Hiromi Tobita 《Angewandte Chemie (International ed. in English)》2016,55(1):188-192
Treatment of pyridine‐stabilized silylene complexes [(η5‐C5Me4R)(CO)2(H)W?SiH(py)(Tsi)] (R=Me, Et; py=pyridine; Tsi=C(SiMe3)3) with an N‐heterocyclic carbene MeIiPr (1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) caused deprotonation to afford anionic silylene complexes [(η5‐C5Me4R)(CO)2W?SiH(Tsi)][HMeIiPr] (R=Me ( 1‐Me ); R=Et ( 1‐Et )). Subsequent oxidation of 1‐Me and 1‐Et with pyridine‐N‐oxide (1 equiv) gave anionic η2‐silaaldehydetungsten complexes [(η5‐C5Me4R)(CO)2W{η2‐O?SiH(Tsi)}][HMeIiPr] (R=Me ( 2‐Me ); R=Et ( 2‐Et )). The formation of an unprecedented W‐Si‐O three‐membered ring was confirmed by X‐ray crystal structure analysis. 相似文献
15.
Alkenes a–d interact at ?80°C in 15 min. with the Vilsmeier reagent (Me2N=CHCl)+PO2Cl2? in presence of 30% H2O2 to yield the corresponding epoxides a–d. The reaction could involve the formation of the highly reactive hydroperoxymethylenedimethylammonium salt (Me2N=CHOOH)+PO2Cl?2. 相似文献
16.
J.M. Klerks G. Van Koten K. Vrieze P. Seignette 《Journal of organometallic chemistry》1981,219(1):9-20
Reaction of [Me2Al{RNS(Me)NR}]2 (R = 2,6-Me2C6H3) with t-BuOH affords N-methylthio-N-(2,6-dimethylphenyl)-2,6-dimethyl-1,4-quinonediimine in 67% yield. The X-ray structure of this compound shows that two conformational isomers are present in the solid. Temperature dependent 13C and 1H NMR measurements show that in solution these conformers exchange at a rate which is fast on the NMR time scale at + 60°C and slow at ?60°C. From the coalescence point of two of the 13C resonances, the free energy of activation is estimated to be 13.7 + 1.0 at 10°C. Possible processes for the exchange are discussed, and also a reaction scheme for the formation of the title compound is discussed. 相似文献
17.
The 29Si, 13C and 1H NMR spectra of mixtures of Me3SiI and Me3SiOSO2CF3 with DMF in CD2Cl2 show signals that are consistent with the formation of Me3SiOH(NMe2)X? but not with penta- or hexa-coordinate silicon species. The spectra of a mixture of Me3SiBr and DMF show a rapidly exchanging, equilibrium mixture of Me3SiOH(NMe2)Br? and starting materials. No strong evidence for salt formation between DMF and Me3SiCl was obtained. The spectra of Me3SiX (X = I, Br, Cl, OSO2CF3) in CD3CN indicate that neither adduct formation nor extra coordination at silicon is significant. 相似文献
18.
Federico G. De las Heras Ana San Félix Ana Calvo-Mateo Piedad Fernández-Resa 《Tetrahedron》1985,41(18):3867-3873
Reaction of methyl 2-acetamido-4,6--benzylidene-2-deoxy-α---hexopyranosid-3-ulose with Me3SiCN afforded methyl 2-acetamido-4,6--benzylidene-3--cyano-2-deoxy-3--trimethylsilyl-α--- Reaction of ethyl 4,6-di--acetyl-2,3-anhydro-α--mannopyranoside with Me3SiCN gave the corresponding ethyl 4,6-di--acetyl-2--cyano-2-deoxy-α--glucopyranoside. Reaction of methyl 4,6--benzylidene-2,3-anhydro-α--allopyranoside or methyl 4,6--benzylidene-2,3-di--tosyl-α--glucopyranoside with Me3SiCN at - 75° or - 50° gave the corresponding methyl 6--[(R)-cyano phenyl methyl]-α--glyco-pyranosides with high or total regio and stereoselectivity. 相似文献
19.
《Journal of organometallic chemistry》1986,311(3):269-280
The reaction of Os3(CO)12 with C5Me5H in boiling decalin gives the complexes (η5-C5Me5)(CO)2OsH and [(η5-C5Me5)(CO)2Os]2. Both compounds were converted into (η5-C5Me5)(CO)2OsP(SiMe3)2 (III) via the intermediate form (η5-C5-Me5)(CO)2OsBr. Complex III was treated with ArC(O)Cl (Ar = Ph, 2,4,6-Me3C6H2) to give mixtures of the phosphaalkenyl complexes (η5-C5Me5)(CO)2OsPC(OSiMe3)(Ar) (IVa, b) and the diacylphosphido complexes (η5-C5Me5)(CO)2-OsP[C(O)Ar]2 (Va, b). Pivaloyl chloride underwent reaction with III to give complex Vc as the only product. The synthesis of the complexes IVa, b includes an E/Z isomerization process. 相似文献
20.
Jörn Müller Corinna Hänsch Joachim Pickardt 《Journal of organometallic chemistry》1983,259(3):C21-C25
Reaction of CH3li with (cod)Ir(mid)Cl (I) (cod = 1,5-cyclooctadiene; mid = 1-methylimidazole) in hexano yields a mixture of two geometric isomers of [(cod)IrL]2 (IIa, IIb) where L is a μ-2,3-dihydro-1H-imidazole-1,2,2-triyl ligand. From the reaction of I with C6H5Li a mixture is obtained of IIa, IIb, and a dinuclear complex containing a dibenzoiridacyclopentadienyl unit; the latter has been characterized crystallographically. 相似文献