共查询到20条相似文献,搜索用时 31 毫秒
1.
Keisham Sarjit Singh Mohan Rao Kollipara 《Journal of organometallic chemistry》2005,690(19):4222-4231
The indenyl and pentamethylcyclopentadienyl ruthenium(II) complexes [(η5-L3)Ru(L2)Cl] (L3 = C9H7, L2 = dppe (1a), L2 = dppm (1b); L3 = C5Me5, L2 = dppe (2a); L2 = dppm (2b) (where, dppe = Ph2PCH2CH2PPh2 and dppm = Ph2PCH2PPh2) reacts with NaN3 to yield the azido complexes [(η5-C9H7)Ru(L2)N3], L2 = dppe (3a), dppm (3b) and [(η5-C5Me5)Ru(L2)N3], L2 = dppe (4a), dppm (4b), respectively. The azido complexes undergo [3 + 2] dipolar cycloaddition reaction with dimethylacetylenedicarboxylate to yield triazole complexes [(η5-C9H7)Ru(L2)(N3C2(CO2Me)2)], L2 = dppe (5a), dppm (5b) and [(η5-C5Me5)Ru(L2)(N3C2(CO2Me)2)], L2 = dppe (6a), dppm (6b), respectively. The complexes were fully characterized on the basis of microanalyses, FT-IR and NMR spectroscopy. The crystal structures of the starting complex (1a) and representative complexes 5a, 5b and 6a have been established by single X-ray study. 相似文献
2.
The reaction of the complex [{(η6-C6Me6)Ru(μ-Cl)Cl}2] 1 with sodium azide ligand gave two new dimers of the composition [{(η6-C6Me6)Ru(μ-N3)(N3)}2] 2 and [{(η6-C6Me6)Ru(μ-N3)Cl}2] 3, depending upon the reaction conditions. Complex 3 with excess of sodium azide in ethanol yielded complex 2. These complexes undergo substitution reactions with monodentate ligands to yield monomeric complexes of the type [(η6-C6Me6)Ru(X)(N3)(L)] {X = N3, Cl, L = PPh3 (4a, 9a); PMe2Ph (4b, 9b); AsPh3 (4c, 9c); X = N3, L = pyrazole (Hpz) (5a); 3-methylpyrazole (3-Hmpz) (5b) and 3,5-dimethyl-pyrazole (3,5-Hdmpz) (5c)}. Complexes 2 and 3 also react with bidentate ligands to give bridging complexes of the type [{(η6-C6Me6)Ru(N3)(X)]2(μ-L)} {X = N3, Cl, L = 1,2-bis(diphenylphosphino)methane (dppm) (6, 10); 1,2-bis(diphenylphosphino)ethane (dppe) (7, 11); 1,2-bis(diphenylphosphino)propane (dppp) (8, 12); X = Cl, L = 4,4-bipyridine (4,4′-bipy) (13)}. These complexes were characterized by FT-IR and FT-NMR spectroscopy as well as by analytical data.The molecular structures of the representative complexes [{(η6-C6Me6)Ru(μ-N3)(N3)}2] 2, [{(η6-C6Me6)Ru(μ-N3)Cl}2] 3,[(η6-C6Me6)Ru(N3)2(PPh3)] 4a and [{(η6-C6Me6)Ru(N3)2}2 (μ-dppm)] 6 were established by single crystal X-ray diffraction studies. 相似文献
3.
The synthesis, characterization and thermal behavior of new monomeric allylpalladium (II) complexes with dichalcogenoamidodiphosphinate anions are reported. The complexes [R = H, R′ = Pri, E = S (1a); R = H, R′ = Pri, E = Se (1b); R = H, R′ = Ph, E = S (1c); R = H, R′ = Ph, E = Se (1d); R = Me, R′ = Pri, E = S (2a); R = Me, R′ = Pri, E = Se (2b); R = Me, R′ = Ph, E = S (2c); R = Me, R′ = Ph, E = Se (2d)] have been prepared by room temperature reaction of [Pd(η3-CH2C(R)CH2)(acac)] (acac = acetylacetonate) with dichalcogenoimidodiphosphinic acids in acetonitrile solution. The complexes have been characterized by multinuclear NMR (1H, 13C{1H}, 31P{1H}, 77Se{1H}), FT-IR and elemental analyses. The crystal structures of complexes 1a, 1d and 2d have been reported and they consist of a six-membered PdE2P2N ring (E = S for 1a and Se for 1d and 2d) and an allyl group, C3H4R(R = H for 1a and 1d and Me for 2d). Thermogravimetric studies have been carried out for few representative complexes. The complexes thermally decompose in argon atmosphere to leave a residue of palladium chalcogenides, which have been characterized by PXRD, SEM and EDS. 相似文献
4.
Sodio C.N. Hsu Howard H.Z. Chen I-Jung Lin Jung-Jung Liu Po-Yu Chen 《Journal of organometallic chemistry》2007,692(17):3676-3684
The reaction of [Cu(NCMe)4](BF4) with equimolar amounts of the tris(substituted-pyrazolyl)methane ligand HCPz3 or HC(3,5-Me2Pz)3 yields the respective salts [Cu(HCPz3)(NCMe)](BF4) (1a) or [Cu(HC(3,5-Me2Pz)3)(NCMe)](BF4) (1). The acetonitrile ligand of 1 can be replaced by prazine, 4,4′-dipyridine or 1,4-diisocyanobenzene to yield related mononuclear complexes [Cu(HC(3,5-Me2Pz)3)(pyrazine)](BF4) (2), [Cu(HC(3,5-Me2Pz)3)(4,4′-bipyridine)] (BF4) (3) or [Cu(HC(3,5-Me2Pz)3)(1,4- CNC6H4NC)](BF4) (7), respectively. A series of binuclear copper(I) complexes {[Cu(HC(3,5-Me2Pz)3)]2(μ -BL)}(BF4)2 (4, BL = pyrazine; 5, BL = 4,4′-dipyridine; 8, BL = 1,4-diisocyanobenzene) were prepared by treating equal molar ratio of 1 with related mononuclear complexes 2, 3 and 7. In addition, binuclear copper(I) complexes were also prepared from treatment of 2 equiv of 1 with the related bridge ligand. Both of 4 and 5 reformed mononuclear starting complex 1 in acetonitrile solution. However, the more robust complex 8 was stable in acetonitrile solutions. The structure of complexes 1a, 4, 5, and 7 were confirmed by X-ray crystallography. The redox properties of 4 and 8 were examined by cyclic voltammetry and exhibited two quasi-reversible waves suggesting that no significant structural reorganization occurs during the redox process on the electrochemical time scale. 相似文献
5.
A series of new triorganotin(IV) pyridinecarboxylates with 6-hydroxynicotinic acid (6-OH-3-nicH), 5-hydroxynicotinic acid (5-OH-3-nicH) and 2-hydroxyisonicotinic acid (2-OH-4-isonicH) of the types: [R3Sn (6-OH-3-nic)·L]n (I) (R = Ph, L = Ph·EtOH, 1; R = Bn, L = H2O·EtOH, 2; R = Me, L = 0, 3; R = n-Bu, L = 0, 4), [R3Sn (5-OH-3-nic)]n (II) (R = Ph, 5; R = Bn, 6; R = Me, 7; R = n-Bu, 8), [R3Sn (2-OH-4-isonic·L)]n (III) (R = Bn, 9, L = MeOH; R = Me, L = 0, 10; R = Ph, 11, L = 0.5EtOH) have been synthesized. All the complexes were characterized by elemental analysis, TGA, IR and NMR (1H, 13C, 119Sn) spectroscopy analyses. Among them, except for complexes 5 and 6, all complexes were also characterized by X-ray crystallography diffraction analysis. Crystal structures show that complexes 1-10 adopt 1D infinite chain structures which are generated by the bidentate O, O or N, O and the five-coordinated tin centers. Significant O-H?O, and N-H?O intermolecular hydrogen bonds stabilize these structures. Complex 11 is a 42-membered macrocycle containing six tin atoms, and forms a 2D network by intermolecular N-H?O hydrogen. 相似文献
6.
Michael T. Beach Timothy G. Larocque Ruiyao Wang 《Journal of organometallic chemistry》2008,693(17):2921-2928
The synthesis of a series of anionic half-sandwich ruthenium-arene complexes [E][RuCl2(η6-p-cymene){PR2(p-Ph3BC6H4)}] (E = Bu4N+: R = Ph, 1a, iPr, 1b or Cy, 1c; E = bis(triphenylphosphine)iminium or PNP+: R = Ph, 1a′, iPr, 1b′ or Cy, 1c′) are reported. X-ray crystallographic studies of 1a′ and 1b′ confirmed the three-legged piano-stool coordination geometry. In solution, complexes 1a-c and 1a′-c′ are proposed to form monomer-dimer equilibria as a result of chloride ligand dissociation. Complexes 1a-c and 1a′-c′ also form the formally neutral zwitterionic complexes [RuCl(L)(η6-p-cymene){PR2(p-Ph3BC6H4)}] (L = pyridine: R = Ph, 2a, iPr, 2b or Cy, 2c; L = MeCN: R = Ph, 3a, iPr, 3b or Cy, 3c) via chloride ligand abstraction using AgNO3 or MeOTf. 相似文献
7.
Govindaswamy Padavattan Tobias Steinke M. Belén Díaz-Valenzuela Frank Rominger 《Journal of organometallic chemistry》2010,695(5):673-5049
Reaction of the dimeric allyl-nickel(II) chloro complex [Ni(η3-C3H5)(μ-Cl)]2 (5) with sulfur donor ligands (L = L10-L13) in the presence of ( = 3,5-(CF3)2C6H3) gives the corresponding cationic mononuclear complexes of the type [Ni(η3-C3H5)(L)2]+ (1-4) [L = L10 = diphenyl sulfide (1); L = L11 = 4,4′-thiodiphenol (2); L = L12 = 4,4′-thio-bis(6-tert-butyl-o-cresol) (3); L = L13 = 4,4′-thio-bis (6-tert-butyl-m-cresol) (4)]. All of these complexes were characterized by elemental analysis and NMR spectroscopy, as well as the representative complex 3 additionally by single-crystal X-ray analysis. In comparison to the known complex [Ni(η3-C3H5)(η6-BHT)][B] (BHT = 3,5-di-tert-butyl-4-hydroxytoluene), the herein described cationic complexes show an increased stability towards water. The activity of the complexes for butadiene polymerization in aqueous emulsions was studied. 相似文献
8.
Reactivity of the ruthenium complexes [Ru(κ3-tptz)(PPh3)Cl2] (1) and [Ru(κ3-tpy)(PPh3)Cl2] (2) [tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine; tpy = 2,2′:6′,2″-terpyridine] with several α-amino acids [glycine (gly); leucine (leu); isoleucine (isoleu); valine (val); tyrosine (tyr); proline (pro) and phenylalanine (phe)] have been investigated. Cationic complexes with the general formulations [Ru(κ3-L)(κ2-L″)(PPh3)]+ (L = tptz or tpy; L″ = gly, leu, isoleu, val, tyr, pro, and phe] have been isolated as tetrafluoroborate salts. The resulting complexes have been thoroughly characterized by analytical, spectral and electrochemical studies. Molecular structures of the representative complexes [Ru(κ3-tptz)(val)(PPh3)]BF4 (6), [Ru(κ3-tpy)(leu)(PPh3)]BF4 (10) and [Ru(κ3-tpy)(tyr)(PPh3)]BF4 (13) have been determined crystallographically. The complexes [Ru(κ3-tptz)(leu)(PPh3)]BF4 (4), [Ru(κ3-tptz)(val)(PPh3)]BF4 (6), [Ru(κ3-tpy)(leu)(PPh3)]BF4 (10) [Ru(κ3-tpy)(tyr)(PPh3)] BF4·3H2O (13) exhibited DNA binding behavior and acted as mild Topo II inhibitors (10-40%). The complexes also inhibited heme polymerase activity of the malarial parasite Plasmodium yoelii lysate. 相似文献
9.
Ivan A. Portnyagin 《Journal of organometallic chemistry》2009,694(19):3149-8653
A series of germylene and stannylene (Me2NCH2CH2O)2E (E = Ge, 1; E = Sn, 2) complexes of group 6 metals and iron carbonyls L·M(CO)n (M = Cr, Mo, W, n = 5 (3-8), n = 4 (9, 10); M = Fe, n = 4 (11, 12)) were prepared. These complexes were characterized by 1H, 13C NMR, FTIR and elemental analysis. Ligand properties of 1 and 2 were compared to PPh3 and dmiy (N,N′-dimethylimidazolin-2-ylidene) using theoretical calculations (PBE/TZ2P) and FTIR. Ligand dissociation energies increase in the order Ph3P < 2∼1 < dmiy, while donor strength rise in the order PPh3 < dmiy < 2 < 1. 相似文献
10.
Reaction of [(η5-C5Me5)MCl4], 1-2 (1: M = Mo and 2: W) with six fold excess of [LiBH4·thf] followed by thermolysis with excess chalcogen powders (S, Se and Te) yielded dichalcomolybda- and tungstaboranes, [(η5-C5Me5M)2B4H4E2], 5-8 (5: M = Mo, E = S; 6: M = Mo, E = Se; 7: M = Mo, E = Te; 8: M = W, E = Se) in modest yields. The geometry of 5-8 resembles a hexagonal bipyramid with a missing connectivity of two chalcogen vertices and a very short cross cage metal-metal bonding. All these new dichalcometallaboranes have been characterized by mass, 1H, 11B, 13C NMR spectroscopy, and the structural types were unequivocally established by crystallographic analysis of compound 6. 相似文献
11.
Five new copper(I)/silver(I) complexes containing 2-aminopyridine, [Cu(μ-Cl)(2-Apy)(PPh3)]2(1), [Ag(μ-Cl)(2-Apy)(PPh3)]2(2), [Ag(μ-Br)(2-Apy)PPh3)]2(3), [Ag(μ-ONO2)(2-Apy)(PPh3)]2(4), [Ag(μ-ONO2)(2-Apy)(AsPh3)]2(5) have been synthesised for the first time. Complexes 1–5 are obtained by the reactions of MX (MX = CuCl for 1; M = Ag for 2–5; X = Cl, Br for 2–3; X = NO3 for 4–5) with the monodentate ligands EPh3 (E = P for 1–4; E = As for 5) and 2-Apy in the molar ratio of 1:1:2 in the mixed solvent of CH2Cl2 and MeOH. Complexes 1–5 are characterised by IR and X-ray diffraction. In 1–5, chloride, bromide and nitrate ions bridge two metal atoms to form dinuclear complexes containing the parallelogram cores M2X2 (M = Cu, Ag). 相似文献
12.
The salts [S(NMe2)3][MF6] (M = Nb, 2a; M = Ta, 2b) and [S(NMe2)3][M2F11] (M = Nb, 2c; M = Ta, 2d) have been prepared by reacting MF5 (M = Nb, 1a; M = Ta, 1b) with [S(NMe2)3][SiMe3F2] (TASF reagent) in the appropriate molar ratio. The solid state structure of 2b has been ascertained by X-ray diffraction. The 1:1 molar ratio reactions of 1a with a variety of organic compounds (L) give the neutral adducts NbF5L [L = Me2CO, 3a; L = MeCHO, 3b; L = Ph2CO, 3c; L = tetrahydrofuran (thf), 3d; L = MeOH, 3e; L = EtOH, 3f; L = HOCH2CH2OMe, 3g; L = Ph3PO, 3h; L = NCMe, 3i] in good yields. The complexes MF5L [M = Nb, L = HCONMe2, 3j; M = Nb, L = (NMe2)2CO, 3k; M = Ta, L = (NMe2)2CO, 3l; M = Nb, L = OC(Me)CHCMe2, 3m] have been detected in solution in admixture with other unidentified products, upon 2:1 molar reaction of 1 with the appropriate reagent L. The ionic complexes [NbF4(tht)2][NbF6], 4a, and [NbF4(tht)2][Nb2F11], 4b, have been obtained by combination of tetrahydrothiophene (tht) and 1a, in 1:1 and 2:3 molar ratios, respectively. The treatment of 1 with a two-fold excess of L leads to the species [MF4L4][MF6] [M = Nb, L = HCONMe2, 5a; M = Ta, L = HCONMe2, 5b; M = Nb, L = thf, 5c; M = Ta, L = thf, 5d; M = Nb, L = OEt2, 5e]. The new complexes have been fully characterised by NMR spectroscopy. Moreover, the revised 19F NMR features of the known compounds MF5L [M = Ta, L = Me2CO, 3n; M = Ta, L = Ph2CO, 3o; M = Ta, L = MePhCO, 3p; M = Ta, L = thf, 3q; M = Nb, L = CH3CO2H, 3r; M = Nb, L = CH2ClCO2H, 3s; M = Ta, L = CH2ClCO2H, 3t], TaF4(acac), TaF4(Me-acac) and [TaF(Me-acac)3][TaF6] (Me-acac = methylacetylacetonato anion) are reported. 相似文献
13.
A series of organotin(IV) complexes with O,O-diethyl phosphoric acid (L1H) and O,O-diisopropyl phosphoric acid (L2H) of the types: [R3Sn · L]n (L = L1, R = Ph 1, R = PhCH22, R = Me 3, R = Bu 4; L = L2, R = Ph 9, R = PhCH210, R = Me 11, R = Bu 12), [R2Cl Sn · L]n (L = L1, R = Me 5, R = Ph 6, R = PhCH27, R = Bu 8; L = L2, R = Me 13, R = Ph 14, R = PhCH215, R = Bu 16), have been synthesized. All complexes were characterized by elemental analysis, TGA, IR and NMR (1H, 13C, 31P and 119Sn) spectroscopy analysis. Among them, complexes 1, 2, 3, 5, 8, 9 and 11 have been characterized by X-ray crystallography diffraction analysis. In the crystalline state, the complexes adopt infinite 1D infinite chain structures which are generated by the bidentate bridging phosphonate ligands and the five-coordinated tin centers. 相似文献
14.
The ortho-metallated complexes [Pd2{κ2(C,C)-C6H4(PPh2CHC(O)C6H5R}2(μ-Cl)2] (R = Ph (1a), NO2 (1b), Br (1c)) were prepared by refluxing equimolar mixtures of Ph3PCHC(O)C6H5R, (R = Ph, NO2, Br) and Pd(OAc)2 in MeOH, followed by an excess of NaCl. The dinuclear complexes (1a-1c) react with silver trifluoromethylsulfonate and bidentate ligands [L = bipy (2,2′-bipyridine), phen (phenanthroline), dppe (bis(diphenylphosphino)ethane), dppp (bis(diphenylphosphino)propane)] giving the mononuclear stabilized orthopalladated complexes in endo position [Pd{κ2(C,C)-C6H4(PPh2CHC(O)R}L](OTf) [R = Ph, L = phen (2a), bipy (3a), dppe (4a), dppp (5a); R = NO2, L = phen (2b), bipy (3b), dppe (4b), dppp (5b); R = Br, L = phen (2c), bipy (3c), dppe (4c), dppp (5c); OTf = trifluoromethylsulfonate anion]. Orthometalation and ylidic C-coordination are demonstrated by an X-ray diffraction study of 2c and 3c. In the structures, the palladium atom shows a slightly distorted square-planar coordination geometry. 相似文献
15.
Ph2SiCl2 and PhMeSiCl2 react with Li2E (E = S, Se, Te) under formation of trimeric diorganosilicon chalcogenides (PhRSiE)3 (R = Ph: 1a-3a, R = Me: cis/trans-4a (E = S), cis/trans-5a (E = Se)). In case of E = S, Se dimeric four-membered ring compounds (PhRSiE)2 (R = Ph: 1b-2b, R = Me: cis/trans-4b (E = S), cis/trans-5b (E = Se)) have been observed as by-products. 1a-5b have been characterized by multinuclear NMR spectroscopy (1H, 13C, 29Si, 77Se, 125Te). Four- and six-membered ring compounds differ significantly in 29Si and 77Se chemical shifts as well as in the value of 1JSiSe.The molecular structures of 2a, 3a and trans-5a reported in this paper are the first examples of compounds with unfused six-membered rings Si3E3 (E = Se, Te). The Si3E3 rings adopt twisted boat conformations. The crystal structure of 3a reveals an intermolecular Te-Te contact of 3.858 Å which yields a dimerization in the solid state. 相似文献
16.
Elisa Palma Ângela Domingos Roger Alberto 《Journal of organometallic chemistry》2004,689(25):4811-4819
The (2-methoxyphenyl)piperazine pharmacophore, a part of the WAY 100635 structure, has been functionalized with phosphinoarylbenzylamide or phosphinoarylbenzylamine chelator groups using propylene or hexylene alkyl chains as linkers (L2-L4). These heterofunctionalized phosphines bearing an arylpiperazine moiety have been used to stabilize rhenium tricarbonyl complexes of the type [Re(CO)3Br(κ2-L)] (4, L = L2; 5, L = L3; 6, L = L4), which have been fully characterized, including by X-ray crystallographic analysis in the case of compounds 4 and 5. These monomeric complexes are six-coordinate, displaying a distorted octahedral coordination geometry with a facial arrangement of the carbonyl groups. The other three remaining positions are occupied by a bromide and by the bidentate heterofunctionalized phosphine, which coordinates through the phosphorus and the oxygen atom or through the phosphorus and the nitrogen atom in 4 and 5, respectively. The 99mTc complexes (3a-6a) were also prepared and their characterization established by comparative HPLC, using the Re complexes as surrogates. The in vitro binding affinity for the 5HT1A receptor subtype and the selectivity against the 5HT2A receptors for the rhenium complexes were determined. Compound 3 is the only one which presents a reasonable affinity and selectively towards 5HT1A (IC50 = 20 nM) and 5HT2A (IC50 = 4680 nM) receptors, respectively. When the spacer length between the chelate unit and receptor binding domain increased and/or the amide group in the chelator was replaced by a secondary amine unacceptable affinity values for 5HT1A receptors (IC50 = 200-1100 nM) and lost of selectivity were observed. 相似文献
17.
Sofia I. Pascu Karl S. Coleman Nicholas H. Rees 《Journal of organometallic chemistry》2005,690(6):1645-1658
Treatment of the bulky iminophosphine ligand [Ph2PCH2C(Ph)N(2,6-Me2C6H3)] (L) with [M(CH3CN)2(ligand)]+n, where for M = Pd(II): ligand = η3-allyl, n = 1, and for M = Rh(I), ligand: 2(C2H4), 2(CO) or cod, n = 0, yields the mono-cationic iminophosphine complexes [Pd(η3-C3H5)(L)][BF4] (1), [Rh(cod)(L)][BF4] (2), [Rh(CO)(CH3CN)(L)][BF4] (3), and cis-[Rh(L)2][BF4] (4). All the new complexes have been characterised by NMR spectroscopy and X-ray diffraction. Complex 1 shows moderate activity in the copolymerisation of CO and ethene but is inactive towards Heck coupling of 4-bromoacetophenone and n-butyl acrylate. 相似文献
18.
Frederik Blank José Ruiz Venancio Rodríguez 《Journal of organometallic chemistry》2011,696(2):473-487
Dinuclear complexes of palladium(II), containing two bridging halogen (Cl or Br) ligands, [NnBu4]2[(X5C6)2Pd(μ-Cl)2Pd(C6X5)2] and [(X5C6)(L)Pd(μ-Y)2Pd(C6X5)(L)] (X = F, Cl; Y = Cl, Br), readily react with cyclopentadienylthallium, C5H5Tl, to give the corresponding air stable half-sandwich, pseudo-trigonal η5-cyclopentadienylpalladium complexes, [NnBu4][(η5-C5H5)Pd(C6X5)2] (X = F 1, Cl 2) and (η5-C5H5)Pd(C6X5)(L) (X = F, L = CNBut3, PPh34, PMe2Ph 5, PEt36, AsPh37, SbPh38; X = Cl, L = PMe2Ph 9, PEt310), respectively. With tetraphenylcyclopentadienylthallium, C5Ph4HTl or pentabenzylcyclopentadienylthallium, C5Bn5Tl (Bn = CH2Ph) the air stable half-sandwich complexes (η5-C5Ph4H)Pd(C6F5)(AsPh3), 12 and (η5-C5Bn5)Pd(C6F5)(AsPh3), 13 are synthesized accordingly. The molecular structures were verified by NMR-spectroscopy, X-ray crystallography (7, 12, 13) and electron impact-mass spectrometry (EI-MS). The precatalysts 4 and 7 can be activated with methylalumoxane (MAO) for the homopolymerization of norbornene (NB) and 5-ethylidene-2-norbornene (ENB) and for the copolymerization of NB with 5-vinyl-2-norbornene (VNB) or ENB with activities of more than 106 gPNB/(molPd·h). The higher activity of 7/MAO over 4/MAO towards NB homopolymerization was reversed when the olefin-substituted VNB or ENB were added. Then, the more strongly bound PPh3 ligand of 4 (versus AsPh3 of 7) can compete with the olefin functionality of VNB or ENB and assume a directing role for the insertion of the ring double bond. As a consequence 4/MAO shows almost the same activity in NB and ENB homopolymerization. 相似文献
19.
Structural diversity in the self-assembly of Ag(I) complexes containing 2-amino-5-halopyrimidine 总被引:1,自引:0,他引:1
Chia-Jun WuChih-Yuan Lin Pei-Chi ChengChun-Wei Yeh Jhy-Der Chen Ju-Chun Wang 《Polyhedron》2011,30(13):2260-2267
A series of Ag(I) complexes containing the 2-amino-5-halopyrimidine ligands have been synthesized and their structures characterized by X-ray crystallography. The isomorphous complexes Ag(L-Cl)2(CF3SO3) (L-Cl = 2-amino-5-chloropyrimidine), 1, and Ag(L-Br)2(CF3SO3) (L-Br = 2-amino-5-bromopyrimidine), 2, are mononuclear, while [Ag(L-Br)(CF3SO3)]6·6C4H10O, 3, and [Ag(L-I)(CF3SO3)]6 (L-I = 2-amino-5-iodopyrimidine), 4, show cyclic self-assembly of six Ag(Ι) atoms and six L-X ligands, resulting in 24-membered metallocycles. The complex [Ag(L-I)(CF3SO3)]∞, 5, forms 1D zigzag chains which are linked through C-I?Ag and Ag?O interactions to form a 3D structure. The tetranuclear complexes [Ag(L-X)(NO3)]4 [X = Cl, 6; Br, 7] form 16-membered metallocycles, while [Ag(L-X)(ClO4)]∞ [X = Cl, 8; Br, 9] exhibit helical chains. The different structure of 5 from 1 and 2 appears to be due to the stronger nucleophilic character of the iodine atom. In these complexes, the relatively smaller NO3− anions lead to the formation of tetranuclear metallocycles and the larger CF3SO3− anions support the hexanuclear metallocycles, whereas the ClO4− anions induce the helical chains. 相似文献
20.
Investigation on coordination modes of organotin(IV) complexes with 6-thiopurine and related ligands
The organotin(IV) complexes R2Sn(tpu)2 · L [L = 2MeOH, R = Me (1); L = 0: R = n-Bu (2), Ph (3), PhCH2 (4)], R3Sn(Hthpu) [R = Me (5), n-Bu (6), Ph (7), PhCH2 (8)] and (R2SnCl)2 (dtpu) · L [L = H2O, R = Me (9); L = 0: R = n-Bu (10), Ph (11), PhCH2 (12)] have been synthesized, where tpu, Hthpu and dtpu are the anions of 6-thiopurine (Htpu), 2-thio-6-hydroxypurine (H2thpu) and 2,6-dithiopurine (H2dtpu), respectively. All the complexes 1-12 have been characterized by elemental, IR, 1H, 13C and 119Sn NMR spectra analyses. And complexes 1, 2, 7 and 9 have also been determined by X-ray crystallography, complexes 1 and 2 are both six-coordinated with R2Sn coordinated to the thiol/thione S and heterocyclic N atoms but the coordination modes differed. As for complex 7 and 9, the geometries of Sn atoms are distorted trigonal bipyramidal. Moreover, the packing of complexes 1, 2, 7 and 9 are stabilized by the hydrogen bonding and weak interactions. 相似文献