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1.
The syntheses and properties of the titanium(III) complexes Cp2Tir · R′CN (R = C6H5, o-, m-, p-CH3C6H4, CH2C6H5, C6F5, Cl; R′ = CH3, t-C4H9, C6H5, o-CH3C6H4, 2,6-(CH3)2C6H3) are described. In the complexes the nitrogen atom of the cyanide ligands is coordinated to the metal. The thermal stabilities of the complexes depend markedly on R and R′; on heating they undergo a novel reaction in which two cyanide ligands are coupled by formation of a CC bond, while the metal is oxidized to titanium(IV).  相似文献   

2.
Zusammenfassung Die Umsetzung von Alkalidiphenylphosphid mit Methylaryl-sulfonaten zu tert. Phosphinen gelingt umso leichter, je weniger Methylgruppen der Arylrest enthält. Folgende Phosphine (C6H5)2PR wurden dargestellt: R=2-CH3C6H4–, 4-CH3C6H4–, 2,4-(CH3)2C6H3– und 4-Methyl--naphthyl. Ebenso wurden die Phosphine mit R=3-(CH3)2NC6H4– und 2-(CH3)2NC6H4– aus den Dimethylanilinsulfonaten erhalten. Die Umsetzung von (C6H5)2PK mit Na-1,4-Chlorbenzolsulfonat im Molverhältnis 2:1 gibt fast quantitativ 1,4-Phenylen-bis-diphenylphosphin, im Molverhältnis 1:1 aber entsteht (bei tieferen Temperaturen) Diphenylphosphin-p-benzolsulfonat. Diphenyl-(2,4,6-trimethyl-phenyl)phosphin wird am besten aus Diphenylchlorphosphin und Mesitylmagnesiumbromid hergestellt.Zusammenfassung Alkali diphenylphosphides react with methylarylsulfonates giving tert. phosphines. The yield increases with decreasing number of methyl groups in the arylsulfonate. The following phosphines (C6H5)2PR were prepared: R=2-CH3C6H4, 4-CH3C6H4, 2,4-(CH3)2C6H3, and 4-methyl--naphthyl. Similarly the phosphines with R=3-(CH3)2NC6H4 and 2-(CH3)2NC6H4 were prepared from dimethylaniline sulfonates. The reaction of (C6H5)2PK with sodium 1,4 chlorophenyl sulfonate at a molar ratio of 2:1 yields nearly quantitatively 1,4-phenylene-bis(diphenylphosphine); however at a mole ratio of 1:1 and at lower temperatures sodium diphenylphosphine-p-phenyl sulfonate is obtained. The best way to prepare diphenyl(2,4,6-trimethyl-phenyl)phosphine was to use diphenyl-chloro phosphine and mesitylmagnesium bromide.  相似文献   

3.
Pentafluorophenyl Compounds of Phosphorus The preparation of compounds of the type R(C6F5)PX (R = CH3, C2H5, t-C4H9 and C6H5: X = F, Cl, Br and N(C2H5)2) is described. These derivatives are converted to trifluorophosphoranes, R(C6F5)PF3, and phosphinic acid fluorides, R(C6H5)P(:O)F. The n.m.r. spectra are discussed.  相似文献   

4.
Dicarbonylcyclopentadienylphenylcarbynemanganese tetrachloroborate, [C5H5(CO)2MnCC6H5] [BCl4], reacts with the isocyanides CH3NC, cyclo-C6H11NC and t-C4H9NC, affording the thermolabile, dark green keteniminyl-complexes [C5H5(CO)2MnC(C6H5)CNR] [BCl4] (R′  CH3, cyclo-C6H11, t-C4H9). A clear stabilisation results when SbCl6- replaces BCl4- as counterion, for example in the salt [C5H5(CO)2MnC(C6H5)CNC4H9] [SbCl6]. The product obtained by the reaction of [C5H5(CO)2ReCCH3] [BCl4] with t-C4H9NC is extremely labile and could up to now only be examined using infrared technique.Under carefully controlled conditions, the t-C4H9 group splits off the manganese product [C5H5(CO)2MnC(C6H5)CNC4H9] [BCl4], yielding the carbene complex C5H5(CO)2MnC(C6H5)CN. Decomposition can be reversed by N-alkylation of the carbene complex with t-C4H9Cl/SbCl5, establishing an alternative synthetic route towards [C5H5(CO)2MnC(C6H5)CNC4H9][SbCl6].  相似文献   

5.
Syntheses of the compounds [Pt(η4-COD)(4-XC6H4)(4-O2NC6H4)] (X = (CH32N, CH3O, CH3, NO2; COD = 1,5-cyclooctadiene) and cis-{Pt[P(C6H53]2- (4-O2NC6H4(4-XC6H4)} (X = CF3, NO2) are reported. Experiments to synthesize cis-{Pt[P(C6H5)3]2(4-O2NC6H4(4-XC6H4} (X = (CH32N, CH3O, CH3) with an electron donor in one and an electron acceptor in the second platinum-bonded phenyl ring resulted in the spontaneous reductive elimination of 4-O2NC6H4C6-H4X-(4). This observation supports the hypothesis of a donor-acceptor interaction in the transition state of the reductive biphenyl elimination.  相似文献   

6.
Reaction of the Schiff base ligand derived from 4-pyridinecarboxaldehyde NC5H4C(H)N[2′,4′,6′-(CH3)C6H2], (1), with palladium(II) acetate in toluene at 60 °C for 24 h gave [Pd{NC5H4C(H)N[2′,4′,6′-(CH3)C6H2]}2(OCOCH3)2], (2), with two ligands coordinated through the pyridine nitrogen. Treatment of the Schiff base ligand derived from 4-pyridinecarboxaldehyde N-oxide, 4-(O)NC5H4C(H)N[2′,4′,6′-(CH3)C6H2], (4), with palladium(II) acetate in toluene at 75 °C gave the dinuclear acetato-bridged complex [Pd{4-(O)NC5H3C(H)N[2′,4′,6′-(CH3)C6H2]}(OCOCH3)]2, (5) with metallation of an aromatic phenyl carbon. Reaction of complex 5 with sodium chloride or lithium bromide gave the dinuclear halogen-bridged complexes [Pd{4-(O)NC5H3C(H)N[2′,4′,6′-(CH3)C6H2]}(Cl)]2, (6) and [Pd{4-(O)NC5H3C(H)N[2′,4′,6′-(CH3)C6H2]}(Br)]2, (7), after the metathesis reaction. Reaction of 6 and 7 with triphenylphosphine gave the mononuclear species [Pd{4-(O)NC5H3C(H)N[2′,4′,6′-(CH3)C6H2]}(Cl)(PPh3)], (8) and [Pd{4-(O)NC5H3C(H)N[2′,4′,6′-(CH3)C6H2]}-(Br)(PPh3)], (9), as air stable solids. Treatment of 6 and 7 with Ph2P(CH2)2PPh2 (dppe) in a complex/diphosphine 1:2 molar ratio gave the mononuclear complexes [Pd{4-(O)NC5H3C(H)N[2′,4′,6′-(CH3)C6H2]}(PPh2(CH2)2PPh2)][Cl], (10), and [Pd{4-(O)NC5H3C(H)N[2′,4′,6′-(CH3)C6H2]}(PPh2(CH2)2PPh2)][PF6], (11), with a chelating diphosphine. The molecular structure of complex 9 was determined by X-ray single crystal diffraction analysis.  相似文献   

7.
Lithioamidines &;{;R′N(Li)C(R)NR′; R = H, CH3, C6H5; R′ = C6H5, p-CH3C6H4&;}; react with anhydrous copper(II) chloride to form [Cu&;{;R′NC(R)NR′&;};2]n complexes, and with anhydrous copper(I) chloride to form [Cu&;{;R′NC(R)NR′&;};]m. The copper(II) complexes are diamagnetic, purple solids, which are air stable in the solid state but very air reactive in solution. Experimental data are consistent with a dimeric or more highly associated structure, and an X-ray structural determination shows [Cu&;{;C6H5NC(C6H5)NC6H5&;};2]2 to be dimeric with four bridging amidino-groups and a short CuCu distance (2.46Å). The copper(I) complexes are pale yellow solids, which in solution are subject to rapid aerial oxidation, especially in the presence of free amidines, and disproportionation to [Cu&;{;R′NC(R)HR′&;};2]n and copper metal. Differences in properties are noted between acetamidino-, benzamidino- and formamidino-complexes, the last complexes of copper(I) being most stable towards disproportionation. Cu&;{;C6H5NC(CH3)NC6H5&;};2 reacts with pyridine (Py) to form the copper(I) derivative Cu&;{;C6H5NC(CH3)NC6H5&;};. 2Py and with carbon disulphide to form Cu&;{;C6H5NC(CH3)NC6H5&;};2.CS2 which is reduced to form Cu&;{;C6H5NC(CH3)NC6H5&;};.CS3.  相似文献   

8.
Contributions to the Chemistry of Transition Metal Alkyl Compounds. XLIII. Tetrakis(alkoxycarbonylmethyl)titanium Compounds Organotitanium(IV) compounds of the type (ROCOCH2)4Ti (R ? C2H5, i-C3H7, t-C4H9, C6H5, C6H5CH2) were obtained by reactions of ROCOCH2Li derivatives with TiCl4 at low temperature. The compounds which decompose only above 90°C were characterized by the hydrolysis products, anaerobic reactions with iodine, and the i.r. spectra. The bond conditions are discussed.  相似文献   

9.
2,4-Bismethylthio-1,3,2,4-dithiadiphosphetane 2,4- disulfide, IIa, is prepared from 0,0-dimethyldithiophosphoric acid, Ia, and P4S10 at 160°C. 2,4-Bis(4-phenoxyphenyl)-1,3,2,4- dithiadiphsophetane 2,4-disulfide, IIc, and 2,4-bis(4-phenylthiolophenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide, IId, are prepared at l60°C from P4 S10 and diphenylether and diphenylsulfides, respectively. Carboxylic acids RCOOH(R = CH3 C2H5, n-C3H7, n-C4H9, C6H5CH2, C6H8) react with compound Ia at 130°C to give the corresponding methyl dithioesters. Carboxylic acids RCOOH (R = C6H8-CH2, C6H8) react with compound Ib at 200°C for 15 min to give the corresponding ethyl dithioesters, while low boiling acids (R = CH3, C2H8, n-C3H7) yielded mixtures of the corresponding ethyl dithioester and ethyl carboxylate. Carboxylic acid chlorides RCOCl (R = ClCH2, C2H5, t-C4H5 C6H5CH2, C6H5, P-NO2C6H4) react with compound IIa at 80°C to give the corresponding methyl dithioesters in good yields. S-Substituted thioesters react with IIC at 85°C to give the corresponding dithioesters in good yields. Dihydro2(3H)-furanone, VI, and 5-methyl-2(3H)-furanone, VII, react with IIa at 80°C; to dihydro-2(3H)-thiophenethione, VIII and 2,2'-dithiobis(5-methyl thiophene),IX, respectively. Also XI reacts with IIa,IIc, and IId to give VIII in nearly quantitative yields.  相似文献   

10.
The positive-ion mass spectra of the following organonitrogen derivatives of metal carbonyls are discussed: (i) The compounds NC5H4CH2Fe(CO)2C5H5, NC5H4CH2COMo(CO)2C5H5, NC5H4CH2W(CO)3C5H5, NC5H4CH2COMn(CO)4, C5H10NCH2CH2Fe(CO)2C5H5, (CH3)2NCH2CH2COFeCOC5H5 and (CH3)2NCH2CH2COMn(CO)4 obtained from metal carbonyl anions and haloalkylamines, (ii) The isocyanate derivative C5H5Mo(CO)3CH2NCO; (iii) The arylazomolybdenum derivatives RN2Mo(CO)2C5H5 (R ? phenyl, p-tolyl, or p-anisyl); (iv) The compound (C6H5N)2COFe2(CO)6 obtained from Fe3(CO)12 and phenyl isocyanate; (v) The N,N,N′,N′-tetramethylethylenediamine complex (CH3)2NCH2CH2N(CH3)2W(CO)4. Further examples of eliminations of hydrogen, CO, and C2H2 fragments were noted. In addition evidence for the following more unusual processes was obtained: (i) Elimination of HCN fragments from the ions [NC5H4CH2MC5H5]+ to give the ions [(C5H5)2M]+ (M ? Fe, Mo and W); (ii) Conversion of C5H5Mo(CO)3CH2NCO to C5H5Mo(CO)2CH2NCO within the mass spectrometer; (iii) Elimination of N2 from [RN2MoC5H5]+ to give [RMoC5H5]+; (iv) Novel eliminations of HNCO, FeNCO, and C6H5NC fragments in the mass spectrum of (C6H5N)2COFe2(CO)6; (v) Facile dehydrogenation of the N,N,N′,-N′-tetramethylethylenediamine ligand in the complex (CH3)2NCH2CH2N(CH3)2W(CO)4.  相似文献   

11.
Some new phosphoramidates were synthesized and characterized by 1H, 13C, 31P NMR, IR spectroscopy and elemental analysis. The structures of CF3C(O)N(H)P(O)[N(CH3)(CH2C6H5)]2 ( 1 ) and 4‐NO2‐C6H4N(H)P(O)[4‐CH3‐NC5H9]2 ( 6 ) were confirmed by X‐ray single crystal determination. Compound 1 forms a centrosymmetric dimer and compound 6 forms a polymeric zigzag chain, both via ‐N‐H…O=P‐ intermolecular hydrogen bonds. Also, weak C‐H…F and C‐H…O hydrogen bonds were observed in compounds 1 and 6 , respectively. 13C NMR spectra were used for study of 2J(P,C) and 3J(P,C) coupling constants that were showed in the molecules containing N(C2H5)2 and N(C2H5)(CH2C6H5) moieties, 2J(P,C)>3J(P,C). A contrast result was obtained for the compounds involving a five‐membered ring aliphatic amine group, NC4H8. 2J(P,C) for N(C2H5)2 moiety and in NC4H8 are nearly the same, but 3J(P, C) values are larger than those in molecules with a pyrrolidinyl ring. This comparison was done for compounds with six and seven‐membered ring amine groups. In compounds with formula XP(O)[N(CH2R)(CH2C6H5)]2, 2J(P,CH2)benzylic>2J(P,CH2)aliphatic, in an agreement with our previous study.  相似文献   

12.
Bulky phosphanes PR3 (R = C6H11, iC3H7, t-C4H9, C6H4CH3-o) stabilize complexes of type [C5H5Ni(PR3)L]BF4 (L=S(CH3)2, (CH3)3PS), from which [C5H5Ni(PR3)2]+ cations are obtained. Iodide replaces the sulfur ligands to yield neutral C5H5Ni(PR3)I compounds. No stable [C5H5Ni(PR3)]+ cations could be obtained by iodide abstraction, but [C5H5Ni(PR3)CO]+ cations were formed in the presence of carbon monoxide.  相似文献   

13.
The following p-substituted N,N-bis-trimethlsilyl anilines p-X? C6H4? N[Si(CH3)3]2 are prepared by silylation of free amines: X = H, CH3, C2H5, CH3O, CH3CO, F, Cl, Br, J, CN, C6HS, (CH3)3SiO, and [(CH3)3Si]2N, and the isotopic derivatives C6H5? 15N[Si(CH3)3]2 and C6D5N[Si(CH3)3]2. The vibrational spectra are reported and assigned. The molecular symmetry of p-[(CH3)3Si]2N? C6H4? N[Si(CH3)3]2 is determined. The influence of the mass of the substituents X on the positions of the νsSiNSi vibrational frequencies is discussed.  相似文献   

14.
The reaction of [Fe(π-C5H5)(CO)2]2 with the dialkyl disulphides R2S2 (R = CH3, C2H5, t-C4H9 or CH2C6H5) affords, as well as dinuclear derivatives of the type [Fe(π-C5H5)(CO)SR]2, trinuclear species of formula [Fe3(π-C5H5)3(CO)2(S)SR].  相似文献   

15.
Synthetic routes for the preparation of 3-alkyl-6-phenyl-4(3H)-pteridinones 6 and their corresponding 8-oxides 5 (R = CH3, C2H5, (CH2)2CH3, (CH2)3CH3, CH(CH3)C2H5, CH(CH3)2 and CH(C2H5)CH2OCH(OC2H5)2 are described and their reactivities towards xanthine oxidase from Arthrobacter M-4 are determined. Only the 3-methyl derivative of 6-phenyl-4(3H)-pteridinone and its 8-oxide i. e. 6a and 5a are found to be substrates although their reactivities are still very low. Oxidation takes place at C-2 of the pteridinone nucleus. All the 3-alkyl derivatives are less tightly bound to the enzyme than 6-phenyl-4(3H)-pteridinone. Introduction of the N-oxide at N-8 considerably lowers the binding of the substrates. Inhibition studies have revealed that 3-methyl-6-phenyl-4(3H)-pteridinone ( 6a ) is a non-competitive inhibitor with a Ki-value of 47 μM and the 3-ethyl derivative ( 6b ) an uncompetitive one with a Ki-value of 19.6 μM.  相似文献   

16.
Deuteration measurements have been made with t-C4H9OK and with 4 moles of CH3COOH mixed with one mole of CF3COOH against 2D-selenophen, 3D-selenophen, 3CH3, 2D-selenophen and 5CH3, 2D-selenophen. Reactivity in the selenohpen-thiopen series is examined via protophilic and electrophilic isotopic-exchange reactions. The factors for the partial exchange rates with acid and base for heterocyclics with D at position 2 and CH3 at position 3, 4, or 5 are compared with those factors for isomers of monodeuterotoluene; it is found that the electronic effect of the CH3 group is transmitted similarly for these heterocyclics and for the benzene ring. Reasonably good agreement is found between the relative constants for deuterium exchange in thiophen, selenophen, and methyl derivatives of these as catalyzed by alkali-metal t-butylates in dimethylsulfoxide (DMSO) and in t-butanol mixed with diethylene glycol dimethyl ether. This shows that the results with DMSO correctly characterize the reactivity in protophilic hydrogen exchange.  相似文献   

17.
Preparation of Fluorosilylsubstituted Hydrazines Fluorosilanes of the type RSiF3 and RR′SiF2 (R = CH3, s-C4H9, t-C4H9, C6H5; R′= CH3, t-C4H9) react with lithium salts of N, N′-trimethylsilyl-phenyl-hydrazine and N, N′-bis- (trimethylsilyl)-hydrazine in a molar ratio 1:1 under formation of fluorosilylsubstituted hydrazines and LiF. The i.r., mass, 1H and 19F n.m.r. spectra of the above mentioned compounds are reported.  相似文献   

18.
Contributions to the Chemistry of Phosphorus. 72. About the Alkyl Cyclomonocarba Phosphanes (PR)4CH2, R = CH3, C2H5, t-C4H9 The alkyl-substituted cyclomonocarbaphosphanes (PR)4CH2 (R = CH3 1 , C2H5 2 , t-C4H9 3 ) are obtained in very good yield by the reaction of the corresponding dipotassium alkylphosphides K2(PR)n (n = 2, 3, 4) with methylene chloride. Besides, small amounts of the homocyclic rings characteristic for the given substituent and of the five-membered cyclodicarbaphosphanes (PR)3(CH2)2 with isolated CH2 groups are formed. For the alkylcyclomonocarbaphosphanes 1 and 2 , configuration isomers could be identified for the first time. The “all-trans” forms are always predominant; the relative amounts of the other isomers decrease strongly with increasing number of cis relationships between the substituents at adjacent phosphorus atoms. The 31P n.m.r. parameters for three of the all together six isomers of 1 distinguishable by n.m.r. spectrometry and for the “all-trans” isomers of 2 and 3 are reported and discussed. A definite separation is possible between substituent and configuration influence on the chemical shifts as well as on the coupling constants.  相似文献   

19.
The reaction of CpFe(CO)2SiCl3 with alcohols yields a partial Cl-OR exchange. By completing the reaction with stoichiometric quantities of the corresponding alcoholate the pure compounds CpFe(CO)2Si(OR)3 (R = CH3, C2H5, n-C3H7, i-C3H7, t-C4H9) can be prepared. Excess of alcoholate splits the FeSi bond yielding the [CpFe(CO)2]-ion. The compounds are characterised by IR and mass spectra.  相似文献   

20.
2,2,6,6-Tetramethylpiperidines with various substituants attached to the C4 atom [R=H, OH, CN, CH2COOH, C6H5, N(CH3)2, N(COCH3)CH2C6H5, N(CH2)5, and N(CH2CH2)O] were studied by means of mass spectrometry. The peculiarities of the fragmentation of the piperidine ring with a shielded electron pair at the heteroatom as a function of the type of substituent attached to the C4, atom are discussed. The fragmentation was studied with the use of high-resolution mass spectrometry, lowvoltage mass spectra, and deuterium labeling.Communication 8 from the series Application of Mass Spectrometry in Structural and Chemical Investigations. See [1] for communication 7.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 507–512, April, 1979.  相似文献   

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