共查询到20条相似文献,搜索用时 15 毫秒
1.
测定了过氧化辛酰(1)和过氧化己酰(2)在邻二氯苯中,分别在碘、碘乙烷、2-碘丙烷和3-溴丙烯存在下,90℃时热分解产物的 1HNMR谱,观察到自由基捕获产物(RX,R=n-C 7H 15、n-C 5H 11;X=I,Br)和歧化产物(R -H)的CIDNP多重效应。讨论了过氧化酰热分解生成自由基对及相互作用的机理。 相似文献
2.
The dinuclear organometallic compounds ((C 5H 5Fe(CO) 2) 2, CO 2(CO) 8 and (C 5H 5NiCO) 2) are oxidized by [(C 5H 5) 2Fe]X (X = BF 4, PF 6) in the presence of neutral ligands L to form the cationic organometallic complexes [C 5H 5Fe(CO) 2L]X, [ trans-Co(CO) 3L 2]X and [C 5H 5NiL 2]X in high yield. 相似文献
3.
Thermal displacement of coordinated nitriles RCN (R = CH 3, C 2H 5 or n-C 3H 7) in [C 5H 5Fe(L 2)(NCR)]X complexes (L 2 = P(OCH 3) 3) 2, (P(OC 6H 5) 3) 2 or (C 6H 5) 2PC 2H 4P(C 6H 5) 2 (DPPE)) by E(CH 3) 2 affords high yields of [C 5H 5Fe(L 2)(E(CH 3) 2)]X compounds (E = S, Se and Te; X = BF 4 or PF 6). Spectroscopic data and ligand displacement reactions are presented and discussed together with related observations on [C 5H 5Fe(CO) 2(E(CH 3) 2)]BF 4 compounds. The molecular structure of [C 5H 5Fe(P(OCH 3) 3) 2(S(CH 3) 2)]PF 6 was determined by a single-crystal X-ray diffraction study: monoclinic, space group P2 1/ n- C52h (No. 14) with a = 8.4064(12), b = 11.183(2), c = 50.726(8) Å, β = 90.672(13)° and Z = 8 molecules per unit cell. The coordination sphere of the iron atom is pseudo-tetrahedral with an Fe---S bond distance of 2.238 Å. 相似文献
4.
Reactions of the extremely labile molybdenocene olefin complexe Mo(η 5-C 5H 5) 2[( Z)-C 6H 5CH=CHC 6H 5] with heteroallenes X=C=Y (X=C=Y = CS 2, ( p-tolyl)NCN( p-tolyl), (C 6H 5) 2CCO) gives the corresponding heteroallene complexes of molybdenocene Mo(η 5-C 5H 5) 2(X=C=Y) in high yields. Spectroscopic data clearly indicate a dihapto-coordination of the heteroallenes via the C=X bond (X = O, S, N). 相似文献
5.
The synthesis of cyclopentadienyl complexes containing polydentate C 5R 4(CH 2CH 2NMe 2) ligands (R = H, Me) and Group 13 elements (Al, Ga, In) is described. The compounds (C 5Me 4CH 2CH 2NMe 2) AlX 2 (X = Me, Cl, Br, I), (C 5Me 4CH 2CH 2NMe 2)MCl 2 (M = Ga, In), (C 5H 4CH 2CH 2NMe 2)AlX 2 (X = H, Me, Et, Cl), (C 5H 4CH 2- CH 2NMe 2)GaCl 2,and (C 5H 4CH 2CH 2NMe 2)InMe 2 are obtained by three different procedures. All compounds that have been characterized, so far, by X-ray diffraction studies show an additional intramolecular coordination of the nitrogen atom in the side chain. Monomeric structures and sufficient volatilities make them potential candidates for MOCVD processes. 相似文献
6.
Liquid crystalline 4-XC 6H 4N=NC 6H 4X-4′ [X = C 4H 9 (1a), C 1OH 21 (1b), OC 4H 9 (1c), OC 8H 17(1d)] can be easily prepared in high yields from the corresponding anilines. In order to study the influence of metals on the thermal properties of these materials, we have obtained adducts [AuCl 3(4-C 4H 9OC 6H 4N=NC 6H 4OC 4H 9-4′)] (2) and [Ag(OC1O 3)L 2] [L = 4-XC 6H 4N=NC 6H 4X-4′; X = OC 4H, (3a), OC 8H 17 (3b)]. The silver adducts show themotropic behaviour. Mercuriation of dialkylazobenzenes 1a-b takes place with [Hg(OAc) 2] and LiCl to give [Hg(R)Cl] [R = C 6H 3(N=NC 6H 4X-4′)-2, X-5; X = C 4H 9 (bpap) (4a), C 10H 21 (dpap) (4b)] while dialkoxyazobenzenes 1c–d require [Hg (OOCCF 3) 2] to obtain [Hg(R)Cl] [R = C 6H 3(N---NC 6H 4X-4′)-2, X-5; X = OC 4H 9 (bxpap) (4c), OC 8H 17 (4d)]. 4a-c react with NaI to give [HgR 2] [R= bpap (5a), dpap (5b), bxpap (5c), oxpap (5d)l. Both chloroaryl-, 4a and 4c, and diaryl-mercurials, 5a and 5c, act readily as transmetailating agents towards [Me 4N] [AuCl 4] in the presence of [Me 4N]Cl to give [Au(η 2-R)Cl 2] [R = bpap (6a), bxpap (6b)]. After reaction of [AuCl 3(tht)] (tht = tetrahydrothiophene) with [Me 4N]Cl and 4b (1:2:1), [Me 4N][Au(dpap)Cl 3] (7) can be isolated. C---H activati bxpap (8b)]. None of the complexes 4–8 shows mesomorphic behaviour. 相似文献
7.
合成与表征了两类14种烷基钴Schiff碱配合物RCo(chel)L(R=CH 3,C 2H 5,n-C 3H 7,n-C 4H 9,i-C 4H 9;chel=salen,SB;L=Py,γ-pic,PPh 3),其中RCo(SB)L是一类新的辅酶B 12模型化合物,五配位的C 2H 5Co(SB)也是首次报道。研究了在固态和溶液中配合物的性质,并讨论了影响配合物中Co─C键稳定性的因素。 相似文献
8.
The study of the reactivity of R---CH=N---(C 6H 4-2-SMe) with R=C 6H 5 or 2,4,6-Me 3-C 6H 2 with palladium(II) salts is reported. These studies have allowed us to prepare and characterize the coordination complexes: cis-[Pd{R---CH=N---(C 6H 4-2-SMe)}Cl 2] {R=C 6H 5 or 2,4,6-Me 3-C 6H 2} and the cyclopalladated compounds [Pd{C 6H 4---CH=N---(C 6H 4-2-SMe)}Cl] and [Pd{(2-CH 2-4,6-Me 2-C 6H 2)---CH=N---(C 6H 4-2-SMe)}Cl]. The X-ray crystal structures of the latter complexes reveal that the thioimines act as a [Csp 2, phenyl,N,S] − and as a [Csp 3, N,S] − terdentate group, respectively. The study of the reactions of the cyclopalladated compounds with PPh 3 is also reported. 相似文献
9.
The EI-mass spectra of the dimeric η 3-allylnickel(II) halides (C 3H 5NiX) 2 (X = Cl, Br, I) were recorded. Besides the successive splitting-off of the C 3H 5 groups and the elimination of C 3H 5X, the formation of NiX 2 leading to (C 3H 5) 2Ni is the predominating fragmentation path. Cleavage of the dimeric structure is observed only in the case where X = I. 相似文献
10.
A series of luminescent rhenium(I) monoynyl complexes, [Re(N---N)(CO) 3(CC---R)] (N---N=bpy, tBu 2bpy; R=C 6H 5, C 6H 4---Cl-4, C 6H 4---OCH 3-4, C 6H 4---C 8H 17-4, C 6H 4---C 6H 5, C 8H 17, C 4H 3S, C 4H 2S---C 4H 3S, C 5H 4N), together with their homo- and hetero-metallic binuclear complexes, {Re(N---N)(CO) 3(CC---C 5H 4N)[M]} (N---N=bpy, tBu 2bpy; [M]=[Re{(CF 3) 2-bpy}(CO) 3]ClO 4, [Re(NO 2-phen)(CO) 3]ClO 4, W(CO) 5) have been synthesized and their electrochemical and photoluminescence behaviors determined. The structural characterization and electronic structures of selected complexes have also been studied. The luminescence origin of the rhenium(I) alkynyl complexes has been assigned as derived states of a [dπ(Re)→π*(N---N)] metal-to-ligand charge transfer (MLCT) origin mixed with a [π(CCR)→π*(N---N)] ligand-to-ligand charge transfer (LLCT) character. The assignments are further supported by extended Hückel molecular orbital (EHMO) calculations, which show that the LUMO mainly consists of π*(N---N) character while the HOMO is dominated by the antibonding character of the Re---CCR moiety resulted from the overlap of the dπ(Re) and π(CCR) orbitals. 相似文献
11.
LnCl 3 (Ln=Nd, Gd) reacts with C 5H 9C 5H 4Na (or K 2C 8H 8) in THF (C 5H 9C 5H 4 = cyclopentylcyclopentadienyl) in the ratio of 1 : to give (C 5H 9C 5H 4)LnCl 2(THF) n (orC 8H 8)LnCl 2(THF) n], which further reacts with K 2C 8H 8 (or C 5H 9C 5H 4Na) in THF to form the litle complexes. If Ln=Nd the complex (C 8H 8)Nd(C 5H 9C 5H 4)(THF) 2 (a) was obtained: when Ln=Gd the 1 : 1 complex [(C 8H 8)Gd(C %H 9)(THF)][(C 8H 8)Gd(C 5H 9H 4)(THF) 2] (b) was obtained in crystalline form. The crystal structure analysis shows that in (C8H8)Ln(C5H9C5H4)(THF)2 (Ln=Nd or Gd), the Cyclopentylcyclopentadieny (η5), cyclooctatetraenyl (η8) and two oxygen atoms from THF are coordinated to Nd3+ (or Gd3+) with coordination number 10. The centroid of the cyclopentadienyl ring (Cp′) in C5H9C5H4 group, cyclooctatetraenyl centroid (COTL) and two oxygens (THF) form a twisted tetrahedron around Nd3+ (or Gd3+). In (C8H8)Gd(C5H9C5H4)(THF), the cyclopentyl-cyclopentadienyl (η5), cyclooctatetraenyl (η8) and one oxygen atom are coordinated to Gd3+ with the coordination number of 9 and Cp′, COT and oxygen atom form a triangular plane around Gd3+, which is almost in the plane (dev. -0.0144 Å). 相似文献
12.
The synthesis of the new (η 2-dppe)(η 5-C 5Me 5)Fe---CC---1,3-(C 6H 4X) ( m-2a/2b; X=F/Br) and (η 2-dppe)(η 5-C 5Me 5)Fe---CC---1,4-(C 6H 4I) (2c) complexes, as well as the solid-state structure of the known (η 2-dppe)(η 5-C 5Me 5)Fe---CC---1,4-(C 6H 4F) (2a) complex are described. The catalytic coupling reactions of the bromo complexes with various alkynes were next investigated. Starting from the known (η 2-dppe)(η 5-C 5Me 5)Fe---CC---1,4-(C 6H 4Br) complex (2b), the synthesis of the (η 2-dppe)(η 5-C 5Me 5)Fe---CC---1,4-(C 6H 4)---CC---H complex (6d) and of the corresponding silyl-protected precursors (η 2-dppe)(η 5-C 5Me 5)Fe---CC---1,4-(C 6H 4)CC---SiR 3 (6b/6c; R= iPr/Me) are reported. By use of lithium---bromine exchange reactions on 2b, the silyl- (7a; E=Si; R=Me) and tin- (7b–7d; E=Sn; R=Me, Bu, Ph) substituted analogues (η 2-dppe)(η 5-C 5Me 5)Fe---CC---1,4-(C 6H 4)ER 3 are also isolated. The spectroscopic and electrochemical characterisations of all these new Fe(II)/Fe(III) redox-active building blocks are presented and the electronic substituent parameters for the “(η 2-dppe)(η 5-C 5Me 5)Fe---CC” group are determined by means of 19F-NMR. 相似文献
13.
Titanium complexes Ti(η 5 : η 1-C 9H 6SiMe 2NCMe 3)X 2(X = Cl, Me, CH 2SiMe 3, CH 2Ph) containing the tert-amino-functionalized indenyl ligand C 9H 6SiMe 3NCMe 3 have been synthesized by the reaction of the dilithium derivative Li 2[C 9H 6SiMe 2NCMe 3 ] with TiCl 3 (THF) 3 followed by oxidation or by the alkylation of the dichloro derivative. Unexpectedly, the reaction of C 9H 6(SiMe 3)(SiMe 2Cl) with TiCl 4 does not give Ti(η 5-C 9H 6SiMe 2Cl)Cl 3. 相似文献
14.
Reaction of R---N=C=N---R (R= p-Me-C 6H 4) and R---P==C=P---R (R=2,4,6- tBu 3C 6H 2) with the di-iron aminocarbene complex [Fe 2(CO) 7{1μ-C(Ph)C(NEt 2)}] (1c) gave corresponding complexes [Fe 2(CO) 6{C(Ph)C(NEt 2)C(NC 6H 4Me)N (C 6H 4Me)}] (2) and [Fe 2(CO) 6{C(Ph)C(NEt 2)C(PC 6H 2tBu 3)P(C 6H 2tBu 3)}] (4), resulting from a coupling reaction with carbon-carbon bond formation. [Fe 2(CO) 5(CNC 6H 4Me){C(Ph)C(NEt 2)N(C 6H 4Me)}], complex 3, obtained in the reaction with R---N=C=N---R, resulted from C=N bond rupture insertion of a nitrene fragment into the Fe=C bond. Complexes 2–4 were characterized by X-ray diffraction. The different geornetries of complexes 2 and 4 are discussed. The formation of these complexes may be explained by cycloaddition on the Fe =C metal-carbene bond. 相似文献
15.
Theoretical calculations (DFT, MP2) are reported for up to four sets of reaction products of trimethylphosphine, (CH 3) 3P, each with H 2O, HCl and HF together with DFT calculations on up to three sets of reaction products of substituted phosphonium cations, (CH 3) 3P–R +. These products comprise (a) P(III) normal complexes (CH 3) 3PHY, (b) P(IV) ‘reverse’ complexes Y(H–CH 2) 3P–R, (c) P(IV) ylidic complexes YHCH 2(CH 3) 2P–R and (d) P(V) covalent compounds Y–P(CH 3) 3–R for Y=HO, Cl and F and R=H, CH 3, C 2H 5, C 2H 4OH and C 2H 4OC:OCH 3. Calculations are carried out at the B3LYP/6-31+G(d,p) level in all cases and also at the MP2/6-31+G(d,p) level for systems in which R=H. Minimum energy structures are determined for predicted complexes or structures and geometrical properties, harmonic vibrations and BSSE corrected binding energies are reported and compared with the limited experimental information available. Potential energy scans predict equilibria between covalent trigonal bipyramidal P(V) forms and reverse complexes comprising hydrogen bonded or ion pair, tetrahedral P(IV) forms separated by low potential energy barriers. Similar scans are also reported for equilibria between reverse complexes and ylidic complexes for Y=OH and R=CH 3, C 2H 5, C 2H 4OH and C 2H 4OC:OCH 3. Corrected binding energies, structures and values of harmonic modes are discussed in relation to bonding The names ‘pholine’ and ‘acetylpholine’ are suggested for phosphorus analogues to choline and acetylcholine. 相似文献
16.
Internal cyclization of a nitrogroup was carried out by heating the N-substituted o-nitroanilines (I; R=C 6H 11---, C 6H 5.CH 2, C 6H 5.CH 2.CH 2---, X=NH) in the presence of ferrous oxalate 1 (Waterman and Vivian's method) as a potential route to partly hydrogenated nitrogen heterocycles. A mechanism for this type of ring-closure is proposed. 相似文献
17.
The reaction of LnCl_3 with K _9H_7(C_9H_7=indenyl)andK_2C_8H_8(C_8H_8=cyclooctatetraene)in tetrahydrofuran(THF)give thecorresponding complexes(η~5-C_9H_7)Ln(η~8-C_8H_8)·2THF.The synthesis of(η~5-C_9H_7)Ln(η~8-C_8H_8)·2THF(Ln=Pr,Nd)and crystal structure of(η~5-C_9H_7)Pr(η~8-C_8H_8)·2THF are described. 相似文献
18.
The preparation of a series of immobilized transition-metal catalysts are reported. The catalysts were obtained by chemisorption of either rhodium(I) or iridium(I) complexes [MX(C 2H 4) 2] n (M = Rh, Ir; X = Cl, OAc, acac, f 3-acac, f 6-acac) on SiO 2 or MgO supports. The oxides were also activated by SiCl 4 or TiCl 4 to give support materials in which the acidic nature of the surface is substantially increased. The activity of the immobilized catalysts was tested, particularly in the reaction of ethene with diphenyldiazomethane which yields a mixture of 1.1-diphenylpropene (8) and 1.1-diphenylcyclopropane (9). It was found that the most active and most selective (highest ratio 8:9) catalyst B1 was formed support material B (SiO 2 activated by SiCl 4) and [RhCl(C 2H 4) 2] 2 (1) and that both the activity and selectivity of B1 was comparable with that of complex 1 in solution. In contrast, the supported catalysts A2, D2 and A3, D3 obtained from [Rh(OAc)(C 2H 4) 2] 2 (2) and [Rh(acac)(C 2H 4) 2] (3) were less active than compounds 2 and 3 in solution. The immobilized catalysts A6, A7, D7 and E7, which were generated from the chloro- and acetatoiridium(I) complexes [IrCl(C 2H 4) 2] 2 (6) and [Ir(OAc)(C 2H 4) 2] 2 (7), possessed a lower activity than the rhodium counterparts. With diazoalkanes other than Ph 2CN 2, the activity of the supported catalyst B1 was partly higher and partly lower than that of complex 1 in the homogeneous phase. 相似文献
19.
The synthesis, characterization and thermal behaviour of several new series of copper(II) complexes derived from carbonylic compounds and their Schiff's bases are reported. The complexes are of two types; [Cu(C 6H 3O( R)-C( X) = O) 2], (type I) and [Cu(C 6H 3O( R)-C( X) = N- R') 2] (type II) where R = - OOC-C 6H 4OC 10H 21- p, and the position of R is 4 or 5; R' = CH 3, n-C 10H 21, p-n-C 10H 21O(C 6H 4)-; X = H, CH 3. In type I complexes, only the compound with X = H and R in position 5 showed mesomorphism. For type II complexes, all the Schiff's bases complexes of copper(II) derived from 2,4-dihydroxybenzaldehyde showed thermotropic mesophases (smectic C and nematic), whereas the complexes derived from 2,5-dihydroxybenzaldehyde were only mesogenic when the imine was derived from methylamine. None of the complexes derived from the ketone (2,4 or 2,5-dihydroxy derivatives) showed liquid-crystalline properties. X-ray studies of four complexes of type II were carried out. The anisotropy of the magnetic susceptibility has a negative sign for complexes with R in position 4 and a positive sign for 2,5-derivative complexes. The relationship between molecular structure and mesomorphic behaviour is discussed. 相似文献
20.
H CIDNP spectra recorded during the decomposition of aliphatic diacyl peroxides ((RCOO)2 R=n-C H (1),n-c5H11(2)) in ODCB in the presence of scavengers,such as I2C2H5I,(CH3)2CHI,and CH2=CHCH2 Br show multiplet effect for the scavenged products,RX(X=Br,I) and for disproportionation products,R-H.The reactionmechanism is discussed in terms of radical pair theory. 相似文献
|