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1.
Bin Li 《Journal of organometallic chemistry》2008,693(1):87-96
Reaction of the doubly bridged dinuclear molybdenum complex (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1) with benzonitrile in refluxing xylene afforded complexes (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)4(μ-η2-η2(⊥)-NCPh)] (2) (50%) and (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)4(μ-η1-η2-NCPh)] (3) (6%) with different coordination of nitrile. The corresponding μ-η2-η2 acetonitrile and propionitrile complexes 4 and 5 could be obtained from the reactions of (Me2C)(Me2Si)(C5H4)2 with (RCN)3Mo(CO)3 (R = Me, Et) in refluxing xylene. Reactions of 1 with isonitriles generated μ-η1-η2-CNR (R = tBu, Ph, C6H11) bridged complexes 6-8 in 53-63% yields. Subsequent reaction of 4 with Ru3(CO)12 yielded two CN bond cleavaged MoRu clusters (Me2C)(Me2Si)(η5-C5H3)2Mo2Ru3(CO)10(μ-CO)(μ3-CMe)(μ4-N) (9) (7%) and [(Me2C)(Me2Si)(η5-C5H3)2]2Mo4Ru6(CO)16(μ-CO)(μ4-CO)2(μ3-η1-η2-η2-NCMe)(μ3-CMe)(μ5-N) (10) (8%). All the new complexes have been fully characterized. The molecular structures of 2, 4, 6, 9, and 10 have been determined by X-ray diffraction analysis. 相似文献
2.
Phosphorus hydrazides PhP(O)[N(Me)NH2]2, (S)P[N(Me)NH2]3, and N3P3[N(Me)NH2]6 were condensed with 7-diethylaminocoumarin-3-aldehyde (RCHO) to afford the corresponding hydrazones PhP(O)[N(Me)NCHR]2 (1), (S)P[N(Me)NCHR]3 (2), and N3P3[N(Me)NCHR]6 (3). The structural characterization of 1-3 was carried out by their HRMS, 1H and 31P{1H} NMR spectra. The molecular structure of 2 was established by a single-crystal X-ray analysis. Interaction of 1 and 2 with various transition metal ions revealed substantial fluorescence enhancement upon interaction with Cu2+ enabling a selective detection mechanism for this metal ion. However, such a fluorescence enhancement was not observed in the case of 3. A 1:1 complex [2·Zn][ClO4]2·4CH2Cl2 was isolated in the reaction of 2 with Zn(ClO4)2·6H2O. The molecular structure of this complex revealed that the ZnII is encapsulated by the ligand utilizing a 3N, 3O coordination set. 相似文献
3.
Wai-Man Cheung Guo-Cang Wang Wa-Hung Leung 《Journal of organometallic chemistry》2011,696(25):4007-4010
Treatment of [Ru(CHR)Cl2(PCy3)2] (Cy = cyclohexyl) with Tl[N(Pr2iPO)2] and AgLOEt (LOEt− = [CpCo{P(O)(OEt)2}3]−) afforded the Ru carbene complexes [Ru(CHPh)(PCy3)Cl{N(Pr2iPO)2}] (1) and [LOEtRu(CHR)(PCy3)Cl] (2), respectively. Chloride abstraction of complex 2 with TlPF6 in MeCN afforded [LOEtRu(CHPh)(PCy3)(MeCN)][PF6] (3). Complexes 1 and 2 are capable of catalyzing ring-closing metathesis of diethyl 1,2-diallylmalonate. The crystal structure of complex 2 has been determined. 相似文献
4.
5.
Reaction of N-(2′-hydroxyphenyl)-4-R-benzaldimines (L-R, R = OCH3, CH3, H, Cl and NO2) with [Os(PPh3)3Br2] in refluxing 2-methoxyethanol in the presence of triethylamine affords two families of organoosmium complexes (1-R and 2-R). In both 1-R and 2-R complexes a benzaldimine ligand is coordinated to the metal center as tridentate C,N,O-donor. In the 1-R complexes, a bidentate N,O-donor imionsemiquinonate ligand, derived from the hydrolysis of another benzaldimine, and a PPh3 ligand are also coordinated to osmium. In the 2-R complexes, a carbonyl, derived from decarbonylation of 4-R-benzaldehyde (derived from the same hydrolysis stated above), and two PPh3 ligands take up the remaining coordination sites on osmium. Structures of the 1-Cl and 2-OCH3 complexes have been determined by X-ray crystallography. All the 1-R and 2-R complexes are diamagnetic, and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry on the 1-R complexes shows a reversible Os(III)-Os(IV) oxidation within 0.47-0.67 V (vs SCE), followed by an irreversible oxidation of the imionsemiquinonate ligand within 1.10-1.36 V. An irreversible Os(III)-Os(II) reduction is also displayed by the 1-R complexes within −1.02 to −1.14 V. Cyclic voltammetry on the 2-R complexes shows a reversible Os(II)-Os(III) oxidation within 0.29-0.51 V, followed by a quasi-reversible oxidation within 1.04-1.29 V, and an irreversible reduction of the coordinated benzaldimine ligand within −1.16 to −1.31 V. 相似文献
6.
Evgeny V. Tretyakov Svyatoslav E. TolstikovGalina V. Romanenko Artem S. BogomyakovDmitry V. Stass Marsil K. KadirovKirill V. Holin Oleg G. SinyashinVictor I. Ovcharenko 《Polyhedron》2011,30(18):3232-3237
An approach to the synthesis of nitronyl nitroxide 2,2′-(buta-1,3-diyne-1,4-diyl)bis(4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole 3-oxide 1-oxyl) (4) was developed. Compound 4 is the first diradical with nitronyl nitroxide groups directly linked through a diacetylene fragment. In solid phase the diradicals are arranged in stacks with parallel CC fragments, with the distances between the terminal carbon atoms of the neighboring diacetylene groups (T and d) being 6.170 and 4.466 Å, respectively, and the angle between the translation vector and the median line passing through the CCCC fragment of 45.9°. The values of T and d are outside the range of structural criteria allowing a topochemical reaction. Thus UV irradiation does not initiate solid phase polymerization of 4. After exposure at 373 K for 1 h the crystals of 4 turn dark-brown, become X-ray amorphous and lose the majority of their paramagnetic centers without significantly changing their mass. Upon further heating up to 400-420 K the product explodes, releasing about 360 kJ/mol of heat. A diluted solution of 4 in 1,4-dioxane produces an EPR spectrum typical of a strong exchange (a multiplet of nine broadened lines with A4N = 0.35 mT), indicating the efficiency of the CCCC fragment as an exchange channel. The character of the experimental μeff(T) dependence for 4 indicates a strong intramolecular antiferromagnetic-type exchange interaction (J/kB ∼ −104 K) and the dominating weak intermolecular ferromagnetic exchange. 相似文献
7.
Makoto Tokunaga Yuki Shirogane Hiroshi Aoyama Yasushi Obora Yasushi Tsuji 《Journal of organometallic chemistry》2005,690(23):5378-5382
A novel CC bond cleavage reaction of aromatic enol ethers (1) to give ketones (2) using molecular oxygen as oxidant is described. Among the examined catalysts (Cu(II), Pd(II), Ru(II), and H+), CuCl2 exhibited the highest activity. The reaction proceeded smoothly with several kinds of substrates. 相似文献
8.
K.R. Kishore Kumar Reddy 《Tetrahedron letters》2008,49(44):6337-6340
Cyclization of 2-[(4-chloroanilino)methyl]phenol (1) with thiophosphoryl chloride afforded 2-chloro-3-(4-chlorophenyl)-3,4-dihydro-2H-1,3,2λ5-benzoxazaphosphinine-2-thione (2). Reaction of 2 with various heterocyclic amines (3) in the presence of Et3N/NaH gave 3-(4-chlorophenyl)-2-nitrogen heterocyclic substituted-3,4-dihydro-2H-1,3,2λ5-benzoxaza-phosphinine-2-thiones (4). Further reaction of 4 with the N-sodium salt of amino heterocyclics in the presence of HCl at 50-60 °C opened the benzoxazaphosphinine ring chemoselectively at the endocyclic P-O bond and yielded 2-[4-chloro(heterocyclic substituted-phosphorothioyl)anilino]methylphenols 5-13. 相似文献
9.
Dafa Chen 《Journal of organometallic chemistry》2006,691(18):3823-3833
Thermal treatment of C9H7SiMe2C9H7 and C9H7Me2SiOSiMe2C9H7 with Ru3(CO)12 in refluxing xylene gave the corresponding diruthenium complexes (E)[(η5-C9H6)Ru(CO)]2(μ-CO)2 [E = Me2Si (1), Me2SiOSiMe2 (2)]. A desilylation product [(η5-C9H7)Ru(CO)]2(μ-CO)2 (3) was also obtained in the latter case. Similar treatment of C9H7Me2SiSiMe2C9H7 with Ru3(CO)12 gave a novel indenyl nonanuclear ruthenium cluster Ru9(μ6-C)(CO)14(μ3-η5:η2:η2-C9H7)2 (5) with carbon-centered tricapped trigonal prism geometry, in addition to the diruthenium complex (Me2SiSiMe2)[(η5-C9H6)Ru(CO)]2(μ-CO)2 (4) and the desilylation product 3. Complex 4 can undergo a thermal rearrangement to form the product [(Me2Si)(η5-C9H6)Ru(CO)2]2 (6). The molecular structures of 1, 2, 4, 5, and 6 were determined by X-ray diffraction. 相似文献
10.
Akira Ando 《Journal of fluorine chemistry》2003,123(2):283-285
The reaction of halothane, 2-bromo-2-chloro-1,1,1-trifluoroethane (1), with aldehydes and ketones in the presence of bases was found to give 1-alkyl- or 1-aryl-2-bromo-2-chloro-3,3,3-trifluoropropanols (2) or 2-chloro-3,3-difluoro-2-propenols (3) selectively in good to moderate yields depending on the bases and reaction conditions. 相似文献
11.
12.
Anna B. DenisovaVyacheslav Ya. Sosnovskikh Wim Dehaen Suzanne ToppetLuc Van Meervelt Vasiliy A. Bakulev 《Journal of fluorine chemistry》2002,115(2):183-192
Reaction of 2-hydrazinothiazoles 1 with 1-thienyl- and 1-furyl-1,3-butanediones 2a,b in methanol in the presence of hydrochloric acid mainly leads to a mixture of pyrazoles 3 and pyrazolines 4 or pyrazoles 3 and 5 in strong acidic conditions. Isomeric hydrazones 6 and pyrazolines 4 were formed and isolated in these reactions in the absence of hydrochloric acid. It has been shown that the regioselectivity in the reaction of diketones 2 with hydrazine 1 is governed by both the concentration of acid and the nature of substituents in the 1,3-diketones 2. Cyclization of hydrazones 6 is shown to occur under milder conditions than dehydration for pyrazolines 4. The new heterocyclic compounds were prepared and fully characterized by NMR spectra and by X-ray analysis for 3c. 相似文献
13.
Sarah McGrandle 《Journal of fluorine chemistry》2005,126(4):449-453
Treatment of N-methylimidazole with pentafluorobenzyl bromide produces 1-pentafluorobenzyl-3-methylimidazolium bromide (1), which reacts with silver(I) oxide to give the N-heterocycle carbene (NHC) complex 1-pentafluorobenzyl-3-methylimidazolin-2-ylidene silver(I) bromide (2). Complex 2 acts as a carbene transfer reagent giving the complexes [(η5-C5Me5)MCl2(NHC)] (3a, M = Rh; 3b M = Ir) on reaction with [(η5-C5Me5)MCl(μ-Cl)]2. An attempt to use intramolecular dehydrofluorinative coupling methodology to link the carbene and the pentamethylcyclopentadienyl ligands of [(η5-C5Me5)RhCl(CNtBu)(NHC)]BF4 was unsuccessful. 相似文献
14.
Frank Tranel 《Journal of fluorine chemistry》2004,125(11):1593-1608
2-Fluoroalk-1-en-3-ols (4), available from terminal alkenes (1) by bromofluorination, subsequent dehydrobromination of the 1-bromo-2-fluoroalkanes (2) to form 2-fluoroalkenes (3) and selenium dioxide mediated allylic oxidation with tert-butylhydroperoxide, undergo Johnson-Claisen rearrangement on treatment with trimethyl orthoacetate to give methyl 4-fluoroalk-4-enoates (7) in high yields. In contrast Ireland-Claisen rearrangement of 3-acetoxy-2-fluorodec-1-ene (9b) with triethylamine and TMSOTf in ether failed. Instead of the expected formation of a carboxylic acid, selective C-silylation of the α-position to the carboxyl group to form 14 occurred. However, Ireland-Claisen rearrangement was successful with corresponding chloroacetates 10 and propionates 11 of four 2-fluoroalk-1-en-3-ols (4) to give 2-chloro-4-fluoroalk-4-enecarboxylic acids (15) or its 2-methyl derivatives 16, respectively, in moderate yields. These [3,3]-sigmatropic rearrangements are diastereoselective giving trans-configured double bonds, exclusively. Corresponding esters derived from (Z)-2-fluorocyclododec-2-enol (22), did rearrange to yield mixtures of diastereomers much less selectively. Also 2-fluorodec-2-enol (6), which was prepared by rearrangement of 2-fluoro-2-octyloxirane (5) with TMSOTf and triethylamine, was successfully applied as a starting material for [3,3]-sigmatropic rearrangements. The corresponding 3-(1-fluoroethenyl)alkanoic acid derivatives 17 and 18 were formed in moderate yield. 相似文献
15.
Fabrice Cottet 《Tetrahedron》2004,60(51):11869-11874
Although there are many conceivable ways to funtionalize, and specifically carboxylate, 2-chloro-4-(trifluoromethyl)pyridine optionally at all three vacant positions, it is more straightforward to prepare only the 2-chloro-4-(trifluoromethyl)pyridine-3-carboxylic acid (1) from this precursor and the other 6-chloro-4-(trifluoromethyl)pyridine-2- and -3-carboxylic acids (2 and 3) from a different one, viz. 5-bromo-2-chloro-4-(trifluoromethyl)pyridine. In the same manner, it proved more convenient to convert 5-chloro-2-(trifluoromethyl)pyridine in only two of the corresponding acids (6 and 7) and to make the third one (8) from 3-bromo-5-chloro-2-(trifluoromethyl)pyridine as an alternative starting material. All model substrates for functionalization were readily accessible from the correspondingly substituted chloroiodopyridine through heavy halogen displacement by in situ generated (trifluoromethyl)copper. 相似文献
16.
Beata Jasiewicz 《Polyhedron》2011,30(10):1703-1709
Cu[(C15H26N2)(OCOR)2] complexes, where OCO is a fragment of either formato or acetato group and C15H26N2 is sparteine or α-isosparteine have been synthesized and structurally characterized. The bis-formato complexes (1 and 2) display a distorted 4 + 1 coordination resulting from variable metal binding stereochemistry and function of the two formato units. The syn formato group acts as a pseudochelating bidentate while the anti conformer as a monodentate ligand. This inequivalence of the two formate ligands seems deliberate for it allows formation of the stabilizing intramolecular hydrogen bond between the CH donor belonging to the monodentate formate ligand and equatorially coordinated oxygen atom belonging to the pseudo-chelating formate ligand. At variance, the C2 symmetrical bis-acetato complex (3) displays tetragonally elongated octahedral geometry of the CuN2O2O′O′ with long off-axis coordination of the second O atom from each acetate ligand in the axial position.Complexes 1-3 have been also characterized by elemental analysis, IR, UV-Vis and MS spectroscopy. 相似文献
17.
William H. Watson Satish G. Bodige Jie Liu 《Journal of organometallic chemistry》2006,691(17):3609-3616
The reaction of the formyl-capped cluster HC(O)CCo3(CO)9 (1) with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) in the presence of added Me3NO leads to the production of the disubstituted cluster HC(O)CCo3(CO)7(bpcd) (2). Thermolysis of 2 in toluene at 60 °C gives the methylidyne-capped cluster HCCo3(CO)7(bpcd) (4) and the phosphido-bridged cluster Co3(CO)7[μ2,η2,η1-P(Ph)CC(PPh2)C(O)CH2C(O)] (5). Cluster 4 has been independently prepared from HCCo3(CO)9 and bpcd and shown to serve as the precursor to 5. The new clusters 2, 4, and 5 have been isolated and characterized in solution by IR and NMR (1H and 31P) spectroscopies and their solid-state structures have been established by X-ray diffraction analyses. Both clusters 2 and 4 contain 48e- and exhibit triangular Co3 cores with a chelating and bridging bpcd ligand in the solid state, respectively. The structure of 5 provides unequivocal support for the loss of the methylidyne capping ligand and P-Ph bond cleavage attendant in the activation of 4 and confirms the presence of the face capping seven-electron μ2,η2,η1-P(Ph)CC(PPh2)C(O)CH2C(O) ligand in the final product. The fluxionality displayed by the bpcd ligand in clusters 2 and 4 and the decarbonylation behavior of the formyl moiety in the former cluster are discussed relative to related alkylidyne-capped Co3 derivatives. 相似文献
18.
Wojciech Dmowski Jolanta Ignatowska Krystyna Piasecka-Maciejewska 《Journal of fluorine chemistry》2004,125(7):1147-1151
Sodium dithionite effectively promotes the addition of 1-bromo-1-chloro-2,2,2-trifluoroethane to the exocyclic double bond of β-pinene. The reaction proceeded in an MeCN/H2O system to give almost quantitatively a 1:1 mixture of diastereoisomers of 4-(2-bromoisopropyl)-1-(2-chloro-3,3,3-trifluoropropyl)-cyclohexene (1). Dehydrobromination of 1 with pyridine gave a mixture of regioisomeric dienes 2 and 3, while treatment with DBU at elevated temperature resulted in total dehydrohalogenation to give trienes 4 and 5. Reduction of 1 with Bu3SnH gave 1-(2-chloro-3,3,3-trifluoropropyl)-4-(isopropyl)cyclohexene (6) which on dehydrochlorination with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) afforded conjugated diene, 4-isopropyl-1-(trans-3,3,3-trifluoropropenyl)-cyclohexene (7), with 50% overall yield. All the transformations proceeded with the retention of configuration at the carbon atom C-4 and the final compound 7 exhibited high optical activity. 相似文献
19.
Nicholas A. Barnes Mark Nieuwenhuyzen Graham C. Saunders 《Journal of fluorine chemistry》2007,128(8):943-951
The trifluorovinyl phosphine complexes [Cp*RhCl2{PR3−x(CFCF2)x}] (1x = 1, a R = Ph, b Pri, c Et; 2x = 2, R = Ph) have been prepared by treatment of [Cp*RhCl(μ-Cl)]2 with the relevant phosphine. The salt [Cp*RhCl(CNBut){PPh2(CFCF2)}]BF4, 3, was prepared by addition of ButNC to 1a in the presence of NaBF4. The salt [Cp*RhCl{κP,κS-(CF2CF)PPh(C6H4SMe-2)}]BF4 was prepared as a mixture of cis (5a) and trans (5b) isomers by treatment of [Cp*RhCl(μ-Cl)]2 with the phosphine-thioether (CF2CF)PPh(C6H4SMe-2), 4, in the presence of NaBF4. The structures of 1a-c and 5a have been determined by single-crystal X-ray diffraction. Intramolecular dehydrofluorinative carbon-carbon coupling between pentamethylcyclopentadienyl and trifluorovinylphosphine ligands of 1a, 3 and 5 has been attempted. No reaction was observed on treatment of the neutral complex [Cp*RhCl2{PPh2(CFCF2)}], 1a, with proton sponge, however, 5a underwent dehydrofluorinative coupling to yield [{η5,κP,κS-(C5Me4CH2CFCF)PPh(C6H4SMe-2)}RhCl]BF4, 6. Other reactions, in particular addition of HF across the vinyl bonds of 5, occurred leading to a mixture of products. The cation of 3 underwent similar reactions. 相似文献