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Raquel Ares Alberto Fernández M. Teresa Pereira Leticia Naya 《Journal of organometallic chemistry》2007,692(20):4197-4208
Treatment of the chloro-bridged dinuclear compounds [{Pd[RC6H3C(H)NCy-C2,N]}(μ-Cl)]2 (R = 4-(COH), 1; R = 5-(COH), 2) with bidentate phosphorus or arsenic diphosphines or diarsine ligands in 1:1 molar ratio gave the dinuclear complexes [{Pd[RC6H3C(H)NCy-C2,N](Cl)}2{μ-(o-Tol)2P(CH2)2P(o-Tol)2}] (R = 4-(COH), 3; R = 5-(COH), 4), [{Pd[RC6H3C(H)NCy-C2,N](Cl)}2{μ-Ph2PC4H2(NH)CH2PPh2}] (R = 4-(COH), 5; R = 5-(COH), 6) and [{Pd[RC6H3C(H)NCy-C2,N](Cl)}2{μ-Ph2As(CH2)2AsPh2}] (R = 4-(COH), 7; R = 5-(COH), 8) with the homobidentate [P,P] and [As,As] ligands in a bridging mode. Treatment of 1 and 2 with the aminophosphine Ph2P(CH2)2NH2 yields the dinuclear complexes [{Pd[RC6H3C(H)NCy-C2,N](Cl)}2{μ-Ph2P(CH2)2NH2}] (R = 4-(COH), 9; R = 5-(COH), 10). The analogous reactions carried out in a 1:2 molar ratio, in the presence of NH4PF6 or NaClO4, gave the mononuclear compounds [Pd{RC6H3C(H)NCy-C2,N}{(o-Tol)2P(CH2)2P(o-Tol)2-P,P}][PF6] (R = 4-(COH), 11; R = 5-(COH), 12), [Pd{RC6H3C(H)NCy-C2,N}{Ph2PC4H2(NH)CH2PPh2-P,P}][ClO4] (R = 4-(COH), 13; R = 5-(COH), 14) and [Pd{RC6H3C(H)NCy-C2,N}{Ph2As(CH2)2AsPh2-As,As}][ClO4](R = 4-(COH), 15; R = 5-(COH), 16), with the [P,P] and [As,As] ligands chelated to the palladium atom.Treatment of 2 with Ph2P(CH2)3NH2 in a 1:2 molar ratio in acetone in the presence of NH4PF6 afforded the mononuclear compound [Pd{5-(COH)C6H3C(H)NCy-C2,N}{Ph2P(CH2)3N(Me2)-P,N}][PF6], 17, via intermolecular condensation between the aminophosphine and the solvent. Condensation was precluded using toluene as solvent to give [Pd{RC6H3C(H)NCy-C2,N}{Ph2P(CH2)nNH2-P,N}][PF6], (n = 3, R = 5-(COH), 18; n = 2, R = 4-(COH), 19; n = 2, R = 5-(COH), 20). Treatment of 1 and 2 with Ph2P(C6H4)CHO in a 1:2 molar ratio in the presence of NH4PF6 gave the mononuclear complexes [Pd{RC6H3C(H)NCy-C2,N}{2-(Ph2P)C6H4CHO-P,O}][PF6] (R = 4-(COH), 21; R = 5-(COH), 22) with the palladium atom bonded to four different atoms (C, N, P, O) and a chelating [P,O] ligand. The crystal structures of compounds 7, 11, 15 and 21 have been determined by X-ray crystallography. 相似文献
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The alkenylaminoallenylidene complex [Ru(η5-C9H7){CCC(NEt2)[C(Me)CPh2]}{κ(P)-Ph2PCH2CHCH2}(PPh3)][PF6] (2) has been prepared by the reaction of the allenylidene [Ru(η5-C9H7)(CCCPh2){κ(P)-Ph2PCH2CHCH2}(PPh3)][PF6] (1) with the ynamine MeCCNEt2. The reaction proceeds regio- and stereoselectively, and the insertion of the ynamine takes place exclusively at the CβCγ bond of the unsaturated chain. The secondary allenylidene [Ru(η5-C9H7){CCC(H)[C(Me)CPh2]}{κ(P)-Ph2PCH2CHCH2}(PPh3)][PF6] (3) is obtained, in a one-pot synthesis, from the reaction of aminoallenylidene 2 with LiBHEt3 and subsequent treatment with silica. Moreover, the addition of an excess of NaBH4 to a solution of the complex 2 in THF at room temperature gives exclusively the alkynyl complex [Ru(η5-C9H7){CCCH2[C(Me)CPh2]}{κ(P)-Ph2PCH2CHCH2}(PPh3)] (5). The heating of a solution of allenylidene derivative 3 in THF at reflux gives regio- and diastereoselectively the cyclobutylidene complex [Ru(η5-C9H7) (PPh3)][PF6](4) through an intramolecular cycloaddition of the CC allyl and the CαCβ bonds in the allenylidene complex 3. The structure of complex 4 has been determined by single crystal X-ray diffraction analysis. 相似文献
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[MBr(CO)5] reacts with m-ethynylphenylamine and pyridine-2-carboxaldehyde in refluxing tetrahydrofuran to give, fac-[MBr(CO)3(py-2-CHN-C6H4-m-(CCH))] (M = Mn, 1a; Re, 2a). The same method affords the tetracarbonyl [Mo(CO)4{py-2-CHN-C6H4-m-(CCH)}] (3a) starting from [Mo(CO)4(piperidine)2]; and the methallyl complex [MoCl(η3-C3H4Me-2)(CO)2{py-2-CHN-C6H4-m-(CCH)}] (4a) from [MoCl(η3-C3H4Me-2)(CO)2(NCMe)2]. The use of p-ethynylphenylamine gives the corresponding derivatives (1b, 2b, 3b, and 4b) with the ethynyl substituent in the para-position at the phenyl ring of the iminopyridine. All complexes have been isolated as crystalline solids and characterized by analytical and spectroscopic methods. X-ray determinations, carried out on crystals of 1a, 1b, 2a, 2b, 3b, 4a, and 4b, reveals the same structural type for all compounds with small variations due mainly to the different size of the metal atoms. The reaction of complexes 1a or 2a with dicobalt octacarbonyl affords the tetrahedrane complexes [MBr(CO)3{py-2-CHN-C6H4-m-{(μ-CCH)Co2(CO)6}}] (M = Mn, 5; Re, 6), the structures of which have been confirmed by an X-ray determination on a crystal of compound 5. 相似文献
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Tushar S. Basu Baul Keisham Surjit Singh Robert Jirásko Anthony Linden 《Journal of organometallic chemistry》2005,690(19):4232-4242
The triphenyltin(IV) complexes of 4-[((E)-1-{2-hydroxy-5-[(E)-2-(2-carboxyphenyl)-1-diazenyl]phenyl}methylidene)amino]aryls (aryls = 4-CH3, 4-Br, 4-Cl, 4-OCH3) have been synthesized and characterized by 1H-, 13C-, 119Sn-NMR, ESI mass spectrometry, IR and 119mSn Mössbauer spectroscopic techniques in combination with elemental analysis. The crystal structures of a representative carboxylate ligand (aryl = 4-CH3) and three Sn complexes, viz., polymeric (Ph3Sn[O2CC6H4{NN(C6H3-4-OH(C(H)NC6H4X-4))}-o])n (X = Me (1) and Br (2)) and dimeric (Ph3Sn[O2CC6H4{NN(C6H3-4-OH(C(H)NC6H4X-4))}-o])2 (X = OMe (4)) complexes are reported. The coordination environment in each complex is trigonal bipyramidal trans-Ph3SnO2. A single zwitterionic carboxylate ligand bridges adjacent Sn atoms via the carboxylate and phenoxide O atoms. 相似文献
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Stanislav Kafka Antonín Klásek Veronika Rosenbreierová Vladimír Mrkvi?ka 《Tetrahedron》2008,64(19):4387-4402
Wittig olefination of 3-aminoquinoline-2,4(1H,3H)-diones 1 with ethyl (triphenylphosphoranylidene)acetate (Ph3PCHCO2Et) afforded (E)-3-amino-4-ethoxycarbonylmethylene-1,2,3,4-tetrahydro-2-quinolones (E)-2 and pyrrolo[2,3-c]quinoline-2,4(3aH,5H)-diones 3. An alternative approach for the synthesis of 3 via 3-bromoacetamidoquinoline-2,4(1H,3H)-diones 7, their corresponding triphenylphosphonium salts 8, and ylides A that undergo intramolecular Wittig reaction, was investigated. Under the applied reaction conditions, the phosphonium salts 8 and ylides A are so unstable that they partly decompose to 3-acetamidoquinoline-2,4(1H,3H)-diones 9 during the synthesis of 3. 相似文献
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Vadapalli Chandrasekhar Mrituanjay D. PandeyBiswanath Das Bani MahantiKandasamy Gopal Ramachandran Azhakar 《Tetrahedron》2011,67(36):6917-6926
Various phosphorus-supported fluorescent probes have been synthesized by the condensation reaction of multi-functional phosphorus hydrazides with various fluorophore-containing carboxaldehydes. Compounds, thus prepared, in this study are (PhO)2P(O)[N(Me)-NCH-R] (1a, 1b), Ph2P(O)[N(Me)-NCH-R] (2b, 2c, 2d), PhP(O)[N(Me)-NCH-R]2 (3b, 3c), P(S)[N(Me)-NCH-R]3 (4b, 4c), P(O)[N(Me)-NCH-R]3 (5a, 5b, 5c), N3P3(O2C12H8)2[N(Me)-NCH-R]2 (6a, 6b, 6c), N3P3(O2C12H8)[N(Me)-NCH-R]4 (7a, 7b, 7c, 7d) and N3P3[N(Me)-NCH-R]6 (8b, 8c), where R=1-pyrenyl (a), 9-anthracenyl (b), 9-phenanthryl (c) and 7-(N,N′-diethylamino)-3-coumarinyl (d). All of these compounds have been characterized by various analytical techniques including 31P{1H} NMR spectroscopy. Compounds 1b, 2b, 3b, 4b, 5b, 5c and 6d have also been characterized by single crystal X-ray analysis. All of these phosphorus-supported compounds exhibit excellent fluorescence properties in aqueous solution at near physiological conditions. 相似文献
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Erika A. Shaffer Alicia M. Beatty Hans-Jörg Schanz 《Journal of organometallic chemistry》2007,692(23):5221-5233
The reaction of (Ph3P)3RuCl2 with 1,1-diphenyl-2-propyn-1-ol was investigated in various solvents. The reaction in thf under reflux is reported to produce the (PPh3)2Cl2Ru(3-phenylindenylidene) complex (3) which has undergone rearrangement of the allenylidene C3-spine. We have improved the reliability of the reported synthesis by adding acetyl chloride which converts the formed water of the reaction and thus increases the acidity of the reaction solution. Without the additive, we observed the exclusive formation of an intermediate of the transformation and identified it as dinuclear (PPh3)2ClRu(μ-Cl)3(PPh3)2RuCCCPh2 complex (5). The reaction of (Ph3P)3−4RuCl2 with 1,1-diphenyl-2-propyn-1-ol in CH2Cl2 or C2H4Cl2 under reflux in the presence of excess conc. aqueous HCl afforded the new, neutral (PPh3)2Cl3RuC-CHCPh2 carbyne complex (7), an HCl adduct of previously elusive (PPh3)2Cl2RuCCCPh2 complex 6 in high yields. In contrast to the formation of complex 3, the reaction in a non-coordinating solvent did not afford the rearrangement of the allenylidene C3-spine. Complex 7 was converted into complex 3 in thf under reflux under loss of a molecule HCl. Complex 7 was converted with triethylamine under loss of HCl to complex 6. Pentacoordinate complex 6 was crystallized in the presence of O-donor ligands (EtOH, MeOH and H2O) to give hexacoordinate (PPh3)2Cl2(ROH)RuCCCPh2 (R = H, CH3, C2H5) complexes (9)-(11) with the O-donor coordinating in trans-position to the allenylidene moiety. The reaction of complex 7 with 2 equiv. of 4-(N,N-dimethylamino)pyridine (DMAP) gave hexacoordinate (PPh3)2Cl2(DMAP)RuCCCPh2complex (12) with one molecule DMAP also coordinating in trans-position to the allenylidene group. Methanol and acetic acid in the absence of strong bases afforded the Fischer-carbene complexes (PPh3)2Cl2RuC(OCH3)-CHCPh2 (14) and (PPh3)2Cl2RuC(OAc)-CHCPh2 (15) where the nucleophile added to the α-carbon atom. The structures of complexes 5, 7, 9-11, 14, and 15 were solved via X-ray crystallography. 相似文献
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Esther Delgado Elisa Hernández Avelino Martín 《Journal of organometallic chemistry》2010,695(3):446-11252
The multifunctional ligands [(Z)-FcCCSC(H)C(H)XR] [X = O, R = Me (2a); X = O, R = Et (2b); X = S, R = Ph (3); X = S, R = C6F5 (5)] and [(Z,Z)-Fc(SR)CC(H)SC(H)C(H)SR] [R = Ph (4), C6F5 (6)] have been prepared through hydroalkoxylation and hydrothiolation processes of the alkyne groups in the compound FcCCSCCH 1. Reactions between compound 3 and the carbonyl metals Co2(CO)8, Os3(CO)10(NCMe)2 and Fe2(CO)9 have allowed the synthesis of the polynuclear compounds [(Z)-{Co2(CO)6}(μ-η2-FcCCSC(H)C(H)SPh)] 9, [(Z)-Os3(CO)9(μ-CO){μ3-η2-FcCCSC(H)C(H)(SPh)}] 10 and [(Z)-{Fe3(CO)9}[μ3,η3-(CCS)-FcCCSC(H)C(H)(SPh)] 11. All the compounds have been characterized by elemental analysis, 1H and 13C{1H} NMR spectroscopy, mass spectrometry and the crystal structure of compounds [(Z)-FcCCSC(H)C(H)OMe] 2a and [{Co2(CO)6}2(μ-η2:η2-FcCCSCCSiMe3)] 7 have been solved by X ray diffraction analysis. 相似文献
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The hydrochlorothiazide, 6-chloro-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide-1,1-dioxide, (HCTZ), widely used as a diuretic and anti-hypertensive drug, was transformed into its N-nitroso-derivative, 6-chloro-4-nitroso-3,4-dihydro-2H-1,2,4-benzothiadiazine-7-sulfonamide-1,1-dioxide (ON-HCTZ) by sodium nitrite in an acidic medium. The crystalline complexes of ON-HCTZ with 18-crown-6 (18C6) and cis-anti-cis-dicyclohexyl-18C6 (DCH6B) demonstrated different H-bonding modes from those present in the co-crystals of HCTZ with the same crown ethers. The influence of the nitroso-group on the binding mode and crystal packing is discussed. 相似文献
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Ethynyl[2.2]paracyclophanes and 4-isocyano[2.2]paracyclophane as ligands in organometallic chemistry
Sébastien Clément Michael Knorr Stefan Dilsky Marta Arroyo 《Journal of organometallic chemistry》2007,692(4):839-850
An alternative synthesis of (±)-4-ethynyl[2.2]paracyclophane (PCPCCH) (5) and 4,16-diethynyl[2.2]paracyclophane (6) via the Corey-Fuchs reaction has been developed. The olefinic intermediate 4-dibromovinyl[2.2]paracyclophane (3) has been isolated and structurally characterized. The racemic terminal alkyne 5 was employed as starting material for assembling of a luminescent extended π-conjugated system containing a thiophene unit and for a catalytic bis-silylation reaction yielding the olefinic dithioether Z-PhSCH2Me2SiC(H)C(PCP)SiMe2CH2SPh (9). The dimetallatetrahedran [Co2(CO)6(μ-η2-PCP-CCH)] (10) has been prepared and its crystal structure determined by an X-ray diffraction analysis. Alkyne 5 has also been used for the preparation of the Pt(0) complex [Pt(PPh3)2(PCPCCH)] (11) and the heterodinuclear dimetallacyclopentenone [(OC)2Fe{μC(O)C(PCP)C(H)}(μ-dppm)Pt(PPh3)] (12). The synthesis and reactivity of 4-isocyano[2.2]paracyclophane (15) towards heterobimetallic iron-platinum and palladium-platinum complexes is also presented. Opening of the dative iron → platinum bond of [(OC)4Fe(μ-dppm)PtCl2] (16) occurred upon addition of 15 to a CH2Cl2 solution of 16 leading to [(OC)4Fe{μ-dppm}PtCl2(CNPCP)] (17). Treatment of [ClPd(μ-dppm)2PtCl] (18) with isocyanide 15 in a 1:1 ratio affords the A-frame compound [ClPd(μ-dppm)2(μ-CNPCP)PtCl] (19), resulting from formal insertion of 15 into the Pd-Pt bond. Addition of 2 equiv. of 15-18 leads to the ionic A-frame compound [ClPd(μ-dppm)2(μ-CNPCP)Pt(CNPCP)]Cl (20). 相似文献
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Concepción López Sonia Pérez Mercè Font-Bardía 《Journal of organometallic chemistry》2005,690(1):228-243
The study of the reactivity of the cyclopalladated complex [Pd{[(η5-C5H3)-CHN-(C6H4-2-SMe)]Fe(η5-C5H5)}Cl] (1c) with the alkynes R1-CC-R1 (with R1 = CO2Me, Ph or Et) is reported.Compound 1c reacts with the equimolar amount of MeO2C-CC-CO2Me in refluxing CH2Cl2 to give [Pd{[(MeO2C-CC-CO2Me)(η5-C5H3)-CHN-(C6H4-2-SMe)]Fe(η5-C5H5)}Cl] (2c), which arises from the monoinsertion of the alkyne into the σ[Pd-C(sp2, ferrocene)] bond.However, when the reaction was performed using Ph-CC-Ph or Et-CC-Et no evidence of the insertion of these alkynes into the σ[Pd-C(sp2, ferrocene)] bond was detected.In contrast with these results, when 1c was treated with the Tl[BF4] followed by the removal of the TlCl formed and the subsequent addition of MeO2C-CC-CO2Me the reaction gave 2c and [Pd{[(MeO2C-CC-CO2Me)2(η5-C5H3)-CHN-(C6H4-2-SMe)]Fe(η5-C5H5)}][BF4] (3c); but when the alkyne was R1-CC-R1 (with R1 = Ph or Et), the ionic palladacycles [Pd{[(R1-CC-R1)2(η5-C5H3)-CHN-(C6H4-2-SMe)]Fe(η5-C5H5)}][BF4] · CH2Cl2 [with R1 = Ph (5c) or Et (6c)] were isolated. In compounds 3c, 5c and 6c, the mode of binding of the butadienyl unit is η3. The reactions of 2c, 3c, 5c and 6c with PPh3 are also reported. The results obtained from these studies reveal that the σ(Pd-S) bond in 2c is more prone to cleave than in 4c-6c. X-ray crystal structures of 2c, 5c and [Pd{[(MeO2C-CC-CO2Me)(η5-C5H3)-CHN-(C6H4-2-SMe)]Fe(η5-C5H5)}Cl(PPh3)] (7c), are also described. Compound 7c arises from 2c by cleavage of the Pd-S bond and the incorporation of a PPh3 in the coordination sphere of the palladium. A parallel study focused on the reactions of [Pd{[2-CH2-4,6-Me2-C6H2]-CHN-(C6H4-2-SMe)}Cl] (1d) (with a [Csp3,N,S]− terdentate group) with the three alkynes reveals that the σPd-C(sp2, ferrocene)] bond of 1c is more reactive than the σ[Pd-C(sp3)] bond of 1d. 相似文献
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Eder do Couto TavaresMarcelo Ribeiro Leite Oliveira Jan JanczakCamila Grossi Vieira Leandro de Carvalho AlvesRodrigo Antunes Castro Lígia Maria Mendonça VieiraRenata Hernandez Lindemann Genivaldo Júlio PerpétuoLeila Léa Yuan Visconte Mayura Marques Magalhães Rubinger 《Polyhedron》2012,31(1):494-501
Four zinc(II)-bis(trithiocarbimato) complexes with the general formula A2[Zn(RSO2NCS3)2] [A = Ph4P+: R = CH3 (1), 4-CH3C6H4 (2); A = Bu4N+: R = CH3 (3), 4-CH3C6H4 (4)] were obtained by the reaction of sulfur with the correspondent zinc(II)-bis(dithiocarbimato) complexes. Additionally, the compound (Ph4P)2[(CH3SO2NCS2)2S)] (5) was prepared from the potassium methylsulfonildithiocarbimate by oxidation with iodine. The compounds were characterized by elemental analyses and IR, 1H NMR and 13C NMR spectroscopies. The compounds 4 and 5 were also characterized by X-ray diffraction techniques. The compound 4 crystallizes in the centrosymmetric space group C2/c of the monoclinic system. The Zn(II) is in a distorted tetrahedral environment (ZnS4) in compound 4, and differ from the coordination mode observed in compound 1, which involves one sulfur and one nitrogen atom of each trithiocarbimate ligand. Compound 5 is the first example of a compound containing a bis(N-alkylsulfonyldithiocarbimate)-sulfide dianion and crystallises in the non-centrosymmetric space group P41212 of the tetragonal system. 相似文献
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Katsuhiko Takeuchi 《Journal of organometallic chemistry》2011,696(6):1156-12481
The reaction of 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne 1 with secondary or primary amines produced amino-substituted disilenes R(R2′N)SiSiHR 2a-d (R = SiiPr[CH(SiMe3)2]2, R2′NEt2N (2a), (CH2CH2)2N (2b), tBu(H)N (2c), and Ph2N (2d)). Spectroscopic and X-ray crystallographic analyses of 2 showed that 2a-c have a nearly coplanar arrangement of the SiSi double bond and the amino group, giving π-conjugation between the SiSi double bond and the lone pair on the nitrogen atom, whereas 2d has a nearly perpendicular arrangement precluding such conjugation. Theoretical calculations indicate that π-conjugation between the π-orbital of the SiSi double bond and the lone pair on the nitrogen atom is markedly influenced by the torsional angle between the SiSi double-bond plane and the amino-group plane. 相似文献