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Haleden Chiririwa Freeman Ntuli Edison Muzenda Alfred Muller 《Transition Metal Chemistry》2013,38(4):393-399
The reactions of N-(2(diphenylphosphino) benzylidene) (phenyl) methanamine, Ph2PPhNHCH2-C5H4N, 1 and N-(2-(diphenylphosphino) (benzylidene) (thiophen-2-yl) methanamine, Ph2PPhNHCH2-C4H3S, 2 with MCl2(cod) and MCl(cod)Me (M = Pd, Pt; cod = 1,5-cyclooctadiene) yield the new complexes [M(Ph2PPhNHCH2-C5H4N)Cl2], M = Pd1a, Pt1b, [M(Ph2PPhNHCH2-C5H4N)ClMe], M = Pd1c, Pt 1d, [M(Ph2PPhNHCH2-C4H3S)Cl2], M = Pd2a, Pt 2b, and [M(Ph2PPhNHCH2-C4H3S)ClMe], M = Pd2c, Pt 2d, respectively. The new compounds were isolated as analytically pure crystalline solids and characterized by 31P-, 1H-NMR, IR spectroscopy, electro spray ionization-mass spectrometry (ESI-MS) and elemental analysis. The representative solid-state molecular structures of the platinum complexes 1b and 2b were determined using single crystal X-ray diffraction analysis and revealed that the complexes exhibit a slightly distorted square-planar geometry. Furthermore, the palladium complexes were tested as potential catalysts in the Heck and Suzuki cross-coupling reactions. 相似文献
3.
Osman Akba Feyyaz Durap Ak?n Baysal Saim Özkar 《Journal of organometallic chemistry》2009,694(5):731-18
Oxidation of N,N,N′,N′-tetrakis(diphenylphosphino)ethylendiamine (1) with elemental sulfur and selenium gives the corresponding sulfide and selenide, respectively, [(Ph2P(E))2NCH2CH2N(P(E)Ph2)2] (E: S 1a, Se 1b). Complexes of 1 [(M2Cl4){(Ph2P)2NCH2CH2N(PPh2)2}] (M: Ni(II) 1c, Pd(II) 1d, Pt(II) 1e) were prepared by the reaction of 1 with NiCl2 or [MCl2(COD)] (M = Pd, Pt). The new compounds were characterized by NMR, IR spectroscopy and elemental analysis. The catalytic activity of Pd(II) complex 1d was tested in the Suzuki coupling reaction and Heck reaction. The palladium complex 1d catalyses the Heck reaction between styrene and aryl bromides as well as Suzuki coupling reaction between phenylboronic acid and arylbromides affording stilbenes and biphenyls in high yield, respectively. 相似文献
4.
Murat Aydemir Akın Baysal Feyyaz Durap Bahattin Gümgüm Saim Özkar Leyla Tatar Yıldırım 《应用有机金属化学》2009,23(11):467-475
The reactions of thiophene‐2‐(N‐diphenylphosphino)methylamine, Ph2PNHCH2‐C4H3S, 1 and thiophene‐2‐[N,N‐bis(diphenylphosphino)methylamine], (Ph2P)2NCH2‐C4H3S, 2, with MCl2(cod) (M = Pd, Pt; cod = 1,5‐cyclooctadiene) or [Cu(CH3CN)4]PF6 yields the new complexes [M(Ph2PNHCH2‐C4H3S)2Cl2], M = Pd 1a, Pt 1b, [Cu(Ph2PNHCH2‐C4H3S)4]PF6, 1c, and [M(Ph2P)2NCH2‐C4H3S)Cl2], M = Pd 2a, Pt 2b, {Cu[(Ph2P)2NCH2‐C4H3S]2}PF6, 2c, respectively. The new compounds were isolated as analytically pure crystalline solids and characterized by 31P‐, 13C‐, 1H‐NMR and IR spectroscopy and elemental analysis. Furthermore, the solid‐state molecular structures of representative palladium and platinum complexes of bis(phosphine)amine, 2a and 2b, respectively, were determined using single crystal X‐ray diffraction analysis. The palladium complexes were tested as potential catalysts in the Heck and Suzuki cross‐coupling reactions. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
5.
Daniel Carmona Roberto Medrano Isabel T. Dobrinovich Fernando J. Lahoz Joaquina Ferrer Luis A. Oro 《Journal of organometallic chemistry》2006,691(26):5560-5566
Half-sandwich complexes of formula [(ηn-ring)MClL]PF6 [L = (S)-2-[(Sp)-2-(diphenylphosphino)ferrocenyl]-4-isopropyloxazoline; (ηn-ring)M = (η5-C5Me5)Rh; (η5-C5Me5)Ir; (η6-p-MeC6H4iPr)Ru; (η6-p-MeC6H4iPr)Os] have been prepared and spectroscopically characterised. The molecular structures of the rhodium and iridium compounds have been determined by X-ray crystallography. The related solvate complexes [(η5-C5Me5)ML(Me2CO)]2+ (M = Rh, Ir) are active catalysts for the Diels-Alder reaction between methacrolein and cyclopentadiene. 相似文献
6.
Raquel Ares Margarita López-Torres Nina Gómez-Blanco Jesús J. Fernández 《Journal of organometallic chemistry》2008,693(24):3655-3667
Treatment of the chloro-bridged dinuclear complex [Pd{3,4-(MeO)2C6H2C(H)N(Cy)-C6,N}(μ-Cl)]2 (1) with homobidentate [P,P], [As,As], [N,N], and heterobidentate [P,As], [P,N] ligands in a 1:1 molar ratio gave the dinuclear complexes [{Pd[3,4-(MeO)2C6H2C(H)N(Cy)-C6,N](Cl)}2{μ-L}] (L = Ph2PC4H6(NH)CH2PPh2 (2); Ph2As(CH2)2AsPh2 (3); 1,3-(NH2CH2)2C6H4 (4); Ph2P(CH2)2AsPh2 (5); Ph2P(CH2)2NH2 (6)), with the bidentate ligands bridging the two cyclometallated fragments.The reaction with the homobidentate ligands in a 1:2 molar ratio in the presence of NaClO4 afforded the mononuclear compounds [[Pd{3,4-(MeO)2C6H2C(H)N(Cy)-C6,N}{L-P,P}][ClO4] (L = Ph2PC4H6(NH)CH2PPh2 (7); (o-Tol)2P(CH2)2P(o-Tol)2 (8)), [Pd{3,4-(MeO)2C6H2C(H)N(Cy)-C6,N}{Ph2As(CH2)2AsPh2-As,As}][ClO4] (9) and [Pd{3,4-(MeO)2C6H2C(H)N(Cy)-C6,N}{L-N,N}][ClO4] (L = NH2(CH2)3NH2 (10); NH2(C6H8)CH2(C6H8)NH2 (11); 1,3-(NH2CH2)2C6H4 (12); 1,3-(NH2)2C5H3N (13); NH2(C6H4)O(C6H4)NH2 (14); NMe2(CH2)2NMe2 (15)), in which the chloro ligands are absent and the bidentate ligands are chelated to the palladium atom.Reaction of 1 with Ph2P(CH2)2AsPh2 in 1:2 molar ratio in acetone in the presence of NH4PF6 afforded the analogous mononuclear compound [Pd{3,4-(MeO)2C6H2C(H)N(Cy)-C6,N}{Ph2P(CH2)2AsPh2-P,As}][PF6] (16); whereas reaction with Ph2P(CH2)3NH2 gave [Pd{3,4-(MeO)2C6H2C(H)N(Cy)-C6,N}{Ph2P(CH2)3N(CMe2)-P,N}][PF6] (17), derived from intermolecular condensation between the aminophosphine and acetone. Condensation of the NH2 group was precluded by change of solvent, using dichloromethane.Iminophoshines also reacted with 1 in 1:2 molar ratio in acetone to give a new series of mononuclear cyclometallated complexes: [Pd{3,4-(MeO)2C6H2C(H)N(Cy)-C6,N}{L-P,N}][ClO4] (L = Ph2PC6H4C(H)NCy (20); Ph2PC6H4C(H)NC(CH3)3 (21); Ph2PC6H4C(H)NNMe2 (22); Ph2PC6H4C(H)NNHMe (23); Ph2PC6H4C(H)NNHPh (24)). Analogous complexes with a stable P,O-chelate were obtained using bidentate [P,O] donor ligands: [Pd{3,4-(MeO)2C6H2C(H)N(Cy)-C6,N}{L-P,O}][Cl] (L = 2-(Ph2P)C6H4CHO (25); Ph2PN(Me)C(O)Me (26)).The crystal structures of compounds 1, 5, 15, 16, 18, 20 have been determined by X-ray crystallography. 相似文献
7.
Several (azido)iridium(III) complexes having a pentamethylcyclopentadienyl (Cp∗) group, [Cp∗Ir(N3)2(Ph2Ppy-κP)] (1: Ph2Ppy = 2-diphenylphosphinopyridine), [Cp∗Ir(N3)(Ph2Ppy-κP,κN)]CF3SO3 (2), [Cp∗Ir(N3)(dmpm)]PF6 (3: dmpm = bis(dimethylphosphino)methane), [Cp∗Ir(N3)(Ph2Pqn)]PF6·CH3OH (4·CH3OH: Ph2Pqn = 8-diphenylphosphinoquinoline), and [Cp∗Ir(N3)(pybim)] (5: Hpybim = 2-(2-pyridyl)benzimidazole) have been prepared and their crystal structures have been analyzed by X-ray diffraction. In complex 1, the Ph2Ppy ligand is only coordinated via the P atom (-κP), while in 2 it acts as a bidentate ligand through the P and N atoms (-κP,κN) to form a four-membered chelate ring. Comparing the structural parameters of the chelate ring in 2 with those of a similar five-membered chelate ring formed by Ph2Pqn in 4, it became apparent that the angular distortion in the Ph2Ppy-κP,κN ring was remarkable, although the Ir–P and Ir–N bonds in the Ph2Ppy-κP,κN ring were not elongated very much from the corresponding bonds in the Ph2Pqn-κP,κN ring. In the pybim complex 5, the five-membered chelate ring was coplanar with the pyridine and benzimidazolyl rings. With the related (azido)iridium(III) complexes analyzed previously, comparison of the structural parameters of the Ir–N3 moiety in [Cp∗IrIII(N3)(L–L′)]+/0 complexes reveals an anomalous feature of the 2,2′-bipyridyl (bpy) complex, [Cp∗Ir(N3)(bpy)]PF6. 相似文献
8.
Sodio C.N. Hsu Shih-Chieh Hu Michael Y. Chiang 《Journal of organometallic chemistry》2009,694(12):1912-7190
The preparation and characterization are described for four ruthenium(II) complexes containing hemilabile phosphine-ether ligand o-(diphenylphosphino)anisole (Ph2PC6H4OMe-o) and/or bidentate ligand diphenylphosphino-phenolate ([Ph2PC6H4O-o]−) Ru(RCN)2(κ2-Ph2PC6H4O-o)2 (1a: R = Me; 1b: R = Et) and [Ru(RCN)2(κ2-Ph2PC6H4O-o)(κ2-Ph2PC6H4OMe-o)](PF6) (2a: R = Me; 2b: R = Et). The ruthenium(II) phosphine-ether complexes undergo mild methyl-oxygen bond cleavage. Two different kinds reaction mechanism are proposed to describe the methyl-oxygen bond cleavage, one involving attack of anionic nucleophiles and another involving the phosphine. The new reactions define novel routes to phosphine-phenolate complexes. The structures of complexes 1a, 1b and 2a were confirmed by X-ray crystallography. 相似文献
9.
《Polyhedron》2005,24(3):391-396
The reaction of [(η5-C5Me5)Ru(PPh3)2Cl] (1) with acetonitrile in the presence of excess NH4PF6 leads to the formation of the cationic ruthenium(II) complex [(η5-C5Me5)Ru(PPh3)2(CH3CN)]PF6 (2). The complex (2) reacts with a series of N,N′ donor Schiff base ligands viz. para-substituted N-(pyrid-2-ylmethylene)-phenylamines (ppa) in methanol to yield pentamethylcylopentadienyl ruthenium(II) Schiff base complexes of the formulation [(η5-C5Me5)Ru(PPh3)(C5H4N-2-CHN-C6H4-p-X)]PF6 [3a]PF6–[3f]PF6, where C5Me5 = pentamethylcylopentadienyl, X = H, [3a]PF6, Me, [3b]PF6, OMe, [3c]PF6, NO2, [3d]PF6, Cl, [3e]PF6, COOH, [3f]PF6. The complexes were isolated as their hexafluorophosphate salts. The complexes were fully characterized on the basis of elemental analyses and NMR spectroscopy. The molecular structure of a representative complex, [(η5-C5Me5)Ru(PPh3)(C5H4N-2-CHN-C6H4-p-Cl)]PF6 [3e]PF6, has been established by X-ray crystallography. 相似文献
10.
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
11.
Swadhin K. Mandal 《Journal of organometallic chemistry》2006,691(13):2969-2977
The chemistry of η3-allyl palladium complexes of the diphosphazane ligands, X2PN(Me)PX2 [X = OC6H5 (1) or OC6H3Me2-2,6 (2)] has been investigated.The reactions of the phenoxy derivative, (PhO)2PN(Me)P(OPh)2 with [Pd(η3-1,3-R′,R″-C3H3)(μ-Cl)]2 (R′ = R″ = H or Me; R′ = H, R″ = Me) give exclusively the palladium dimer, [Pd2{μ-(PhO)2PN(Me)P(OPh)2}2Cl2] (3); however, the analogous reaction with [Pd(η3-1,3-R′,R″-C3H3)(μ-Cl)]2 (R′ = R″ = Ph) gives the palladium dimer and the allyl palladium complex [Pd(η3-1,3-R′,R″-C3H3)(1)](PF6) (R′ = R″ = Ph) (4). On the other hand, the 2,6-dimethylphenoxy substituted derivative 2 reacts with (allyl) palladium chloro dimers to give stable allyl palladium complexes, [Pd(η3-1,3-R′,R″-C3H3)(2)](PF6) [R′ = R″ = H (5), Me (7) or Ph (8); R′ = H, R″ = Me (6)].Detailed NMR studies reveal that the complexes 6 and 7 exist as a mixture of isomers in solution; the relatively less favourable isomer, anti-[Pd(η3-1-Me-C3H4)(2)](PF6) (6b) and syn/anti-[Pd(η3-1,3-Me2-C3H3)(2)](PF6) (7b) are present to the extent of 25% and 40%, respectively. This result can be explained on the basis of the steric congestion around the donor phosphorus atoms in 2. The structures of four complexes (4, 5, 7a and 8) have been determined by X-ray crystallography; only one isomer is observed in the solid state in each case. 相似文献
12.
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
13.
Reaction of thiophene-2-methylamine with one or two equivalents of PPh2Cl in the presence of NEt3, proceeds in thf to give thiophene-2-(N-diphenylphosphino)methylamine, 1a and thiophene-2-(N,N-bis(diphenylphosphino))methylamine, 2a respectively, under anaerobic conditions. Oxidations of 1a and 2a with aqueous hydrogen peroxide, elemental sulfur or gray selenium in thf gives the corresponding oxides, sulfides and selenides [Ph2P(E)NHCH2-C4H3S] (E: O 1b, S 1c, Se 1d) and [(Ph2P(E))2NCH2-C4H3S], (E: O 2b, S 2c, Se 2d) respectively, in high yield. Furthermore, two novel Ru(II) complexes with the P-N ligands 1a and 2a were synthesized starting with the complex [Ru(η6-p-cymene)(μ-Cl)Cl]2. The complexes were fully characterized by analytical and spectroscopic methods. 31P-{1H} NMR, DEPT, 1H-13C HETCOR or 1H-1H COSY correlation experiments were used to confirm the spectral assignments. The molecular structure of thiophene-2-(N-diphenylthiophosphino)methylamine was also elucidated by single-crystal X-ray crystallography. Following activation by NaOH, compounds 3 and 4 catalyze the transfer hydrogenation of acetophenone derivatives to 1-phenylethanol derivatives in the presence of iso-PrOH as the hydrogen source. [Ru(Ph2PNHCH2-C4H3S)(η6-p-cymene)Cl2], 3 and [Ru((PPh2)2NCH2-C4H3S)(η6-p-cymene)Cl]Cl, 4 complexes are suitable catalyst precursors for the transfer hydrogenation of acetophenone derivatives in 0.1 M iso-PrOH solution. Notably 4 acts as an excellent catalyst giving the corresponding alcohols in excellent conversions up to 99% (TOF ? 744 h−1). This transfer hydrogenation is characterized by low reversibility under the experimental conditions. 相似文献
14.
Raquel S. AmimMarcelo R.L. Oliveira Jan JanczakMayura M.M. Rubinger Lígia M.M. VieiraLeandro C. Alves Laércio Zambolim 《Polyhedron》2011,30(5):683-689
Four new compounds of the general formula: (Ph4P)2[Zn(RSO2NCS2)2] where Ph4P = tetraphenylphosphonium cation, R = 4-FC6H4 (1), 4-ClC6H4 (2), 4-BrC6H4 (3) and 4-IC6H4 (4), were obtained by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate (RSO2NCS2K2) with zinc(II) acetate dihydrate in dimethylformamide. All compounds crystallize in the centrosymmetric space group of the triclinic system. The compounds 2, 3 and 4 are isostructural but compound 1 crystallizes as hemihydrate. The elemental analyses and the IR, 1H NMR and 13C NMR data for 1-4 are consistent with the formation of bis(dithiocarbimato)zinc(II) complexes. These compounds are active against the phytopathogenic fungus Colletotrichum gloeosporioides. 相似文献
15.
Hsi-Ying Hsieh Ching-Wen Cheng Fuh-An Yang Jyh-Horung Chen Jo-Yu Tung Shin-Shin Wang Lian-Pin Hwang 《Polyhedron》2007
The reaction of PhHgOAc with N-NHCO-2-C4H3S-Htpp (5) and N-p-HNSO2C6H4tBu-Htpp (4) gave a mercury (II) complex of (phenylato) (N-2-thiophenecarboxamido-meso-tetra phenylporphyrinato)mercury(II) 1.5 methylene chloride solvate [HgPh(N-NHCO-2-C4H3S-tpp) · CH2Cl2 · 0.5C6H14; 6 · CH2Cl2 · 0.5C6H14] and a bismercury complex of bisphenylmercury(II) complex of 21-(4-tert-butyl-benzenesulfonamido)-5,10,15,20-tetraphenylporphyrin, [(HgPh)2(N-p-NSO2C6H4tBu-tpp); 7], respectively. The crystal structures of 6 · CH2Cl2 · 0.5C6H14 and 7 were determined. The coordination sphere around Hg(1) in 6 · CH2Cl2 · 0.5C6H14 and Hg(2) in 7 is a sitting-atop derivative with a seesaw geometry, whereas for the Hg(1) in 7, it is a linear coordination geometry. Both Hg(1) in 6 · CH2Cl2 · 0.5C6H14 and Hg(2) in 7 acquire 4-coordination with four strong bonds [Hg(1)–N(1) = 2.586(3) Å, Hg(1)–N(2) = 2.118(3) Å, Hg(1)–N(3) = 2.625(3) Å, and Hg(1)–C(50) = 2.049(4) Å for 6 · CH2Cl2 · 0.5C6H14; Hg(2)–N(1) = 2.566(6) Å, Hg(2)–N(2) = 2.155(6) Å, Hg(2)–N() = 2.583(6) Å, and Hg(2)–C(61) = 2.064(7) Å for 7]. The plane of the three pyrrole nitrogen atoms [i.e., N(1)–N(3)] strongly bonded to Hg(1) in 6 · CH2Cl2 · 0.5C6H14 and to Hg(2) in 7 is adopted as a reference plane 3N. For the Hg2+ complex in 6 · CH2Cl2 · 0.5C6H14, the pyrrole nitrogen bonded to the 2-thiophenecarboxamido ligand lies in a plane with a dihedral angle of 33.4° with respect to the 3N plane, but for the bismercury(II) complex in 7, the corresponding dihedral angle for the pyrrole nitrogen bonded to the NSO2C6H4tBu group is found to be 42.9°. In the former complex, Hg(1)2+ and N(5) are located on different sides at 1.47 and −1.29 Å from its 3N plane, and in the latter one, Hg(2)2+ and N(5) are also located on different sides at −1.49 and 1.36 Å form its 3N plane. The Hg(1)?Hg(2) distance in 7 is 3.622(6) Å. Hence, no metallophilic Hg(II)?Hg(II) interaction may be anticipated. NOE difference spectroscopy, HMQC and HMBC were employed to unambiguous assignment for the 1H and 13C NMR resonances of 6 · CH2Cl2 · 0.5C6H14 in CD2Cl2 and 7 in CDCl3 at 20 °C. The 199Hg chemical shift δ for a 0.05 M solution of 7 in CDCl3 solution is observed at −1074 ppm for Hg(2) nucleus with a coordination number of four and at −1191 ppm for Hg(1) nucleus with a coordination number of two. The former resonance is consistent with that chemical shift for a 0.01 M solution of 6 in CD2Cl2 having observed at −1108 ppm for Hg(1) nucleus with a coordination number of four. 相似文献
16.
Bahattin Yalçın Perizad A. Fatullayeva Orhan Büyükgüngör Başak Koşar Sülin Taşcıoğlu Akif I. Israfilov Zaur D. Ibayev Ajdar A. Medjidov Adnan Aydın 《Polyhedron》2007
N-(2-Hydroxybenzyl)aminopyridines (Li) react with Cu(II) and Pd(II) ions to form complexes in the compositions Cu(Li)2(CH3COO)2 · nH2O (n = 0, 2, 4), Pd(Li)2Cl2 · nC2H5OH (n = 0, 2) and Pd(L2)2Cl2 · 2H2O. In the complexes, the ligands are neutral and monodentate which coordinate through pyridinic nitrogen. Crystal data of the complexes obtained from 2-amino pyridine derivative have pointed such a coordinating route and comparison of the spectral data suggests the validity of similar complexation modes of other analog ligands. Cu(II) complex of N-(2-hydroxybenzyl)-2-aminopyridine (L1), [Cu(L1)2(CH3COO)2] has slightly distorted square planar cis-mononuclear structure which is built by two oxygen atoms of two monodentate carboxylic groups disposed in cis-position and two nitrogen atoms of two pyridine rings. The remaining two oxygen atoms of two carboxylic groups form two Cu and H bridges containing cycles which joint at same four coordinated copper(II) ion. IR and electronic spectral data and the magnetic moments as well as the thermogravimetric analyses also specify on mononuclear octahedric structure of complexes [Cu(L2)2(CH3COO)2 · 2H2O] and [Cu(L3)2(CH3COO)2 · 4H2O] where L2 and L3 are N-(2-hydroxybenzyl)-2- or 3-aminopyridines, respectively. 相似文献
17.
Trimethylstannyl (diphenylphosphino)acetate (1), which is readily accessible from potassium (diphenylphosphino)acetate and trimethylstannyl chloride, may serve as the source of (diphenylphosphino)acetate anion in the preparation of coordination compounds. Thus, the reactions between [M(cod)Cl2] (M = Pd and Pt; cod = η2:η2-cycloocta-1,5-diene) and two equivalents of 1 give [M(Ph2PCH2CO2-κ2O,P)2] (2 and 3), while the reaction of [{Pd(μ-Cl)Cl(PFur3)}2] (4; Fur = 2-furyl) with one equivalent of 1 yields [SP-4-3]-[PdCl(Ph2PCH2CO2-κ2O,P)(PFur3)] (5). The reactions of 1 with the dimers [{Rh(η5-C5Me5)Cl(μ-Cl)}2] and [{Ru(η6-1,4-MeC6H4(CHMe2))Cl(μ-Cl)}2] (at 1-to-metal ratio 1:1) produce O,P-chelated complexes as well, albeit as stable adducts with the liberated Me3SnCl: [RhCl(η5-C5Me5)(Ph2PCH2CO2-κ2O,P)] · Me3SnCl (6) and[RuCl(η6-1,4-MeC6H4(CHMe2))(Ph2PCH2CO2-κ2O,P)] · Me3SnCl (8). The related complexes with P-monodentate (diphenylphosphino)acetic acid, [RhCl2(η5-C5Me5)(Ph2PCH2CO2H-κ,P)] (7) and [RuCl2(η6-1,4-MeC6H4(CHMe2))(Ph2PCH2CO2H-κP)] (9), were obtained by bridge splitting in the dimers with the phosphinocarboxylic ligand. All new compounds were characterized by spectral methods and combustion analyses, and the structures of 2 · 3CH2Cl2, 3, 4, 5, 6 and 8 were determined by X-ray crystallography. 相似文献
18.
Maria Agostina Cinellu Fabio Cocco Sergio Stoccoro Mario Manassero 《Journal of organometallic chemistry》2009,694(18):2949-47
Reaction of Na[AuCl4] with 2-vinylpyridine (vinpy) and 2-ethylpyridine (etpy) affords the N-bonded adducts Au(Rpy)Cl3 (R = CH2CH, vinpy; CH3CH2, etpy). Cationic adducts, [Au(vinpy)2Cl][X]2 (X = BF4, PF6) and [Au(etpy)2Cl2][BF4], were also obtained by reaction of Au(Rpy)Cl3 with Rpy (1:1) and excess NaBF4 or KPF6. Thermal activation of Au(vinpy)Cl3 in water gives the five-membered cycloaurated derivative [Au(k2-C,N-CH2CH(Cl)-C5H4N)Cl2] formally resulting through a trans nucleophilic addition of a chloride onto the CC bond. No cyclometallated derivatives are obtained by reactions of Au(etpy)Cl3. An X-ray crystal structure determination on the PPh3 derivative [Au(k2-C,N-CH2CH(Cl)-C5H4N)(PPh3)Cl][PF6] was carried out. 相似文献
19.
Helio G. Bonacorso Rosália Andrighetto Nilo Zanatta Marcos A.P. Martins 《Tetrahedron letters》2010,51(29):3752-3755
The unexpected results of the cyclization reactions of N,N′-bis(oxotrifluoroalkenyl)-1,3-phenylenediamines [1,3-C6H4-(NHCRCHC(O)CF3)2], where R = H, Me, and Ph, in a strongly acidic medium (PPA), allowing the synthesis of new trifluoromethylated heterocycles containing the 1,7-phenanthroline nucleus in 32-40% yields and 7-aminoquinolines (38-40% yields), is reported. The bis-enaminoketone intermediates were easily isolated from the reactions of 4-alkoxy-4-alkyl(aryl)-1,1,1-trifluoroalk-3-en-2-ones with 1,3-phenylenediamine in ethanol under mild conditions (68-86% yields). 相似文献
20.
Angel García-Raso Juan J. Fiol Andrés Tasada Francisca M. Albertí Ferran Bádenas Xavier Solans Mercè Font-Bardia 《Polyhedron》2007
The reaction of N9,N9′-(tri or tetramethylene)-bisadenines (Ade2Cx; x = 3 or 4) in HCl 2 M at 50 °C with MCl2 · 2H2O [M = Zn(II), Cd(II)] yields outer sphere compounds like the previously described [(H-Ade)2C3][ZnCl4] · H2O (3) and [(H-Ade)2C3]2[Cd2Cl8(H2O)2] · 4H2O (4) for Ade2C3 and the new {[(H-Ade)2C4][Cd2Cl6(H2O)2] · 2H2O}n (5) for Ade2C4. On the other hand, only in case of Zn(II) complexes by changing [HCl] to 0.1 M, the inner sphere compounds [H-(Ade)2C3(ZnCl3)] (6) and [H-(Ade)2C4(ZnCl3)] · 1.5H2O (7) are obtained. X-ray diffraction study of compound 6, which represents the first inner sphere complex with a N9,N9′-bisadenine, shows a zwitterionic form with one adenine ring protonated at N(1) while the other ring is coordinated via N(7) to a ZnCl3 moiety as in other alkyl-adenine derivatives. In addition, with Ade2C4, is also possible to obtain another inner sphere complex: [(H-Ade)2C4(ZnCl3)2] · 3H2O (8). 相似文献