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1.
Treatment of [MI2(CO)3(NCMe)2] with two equivalents of 4,4-bipyridine (4,4-bipy) in CH2Cl2 at room temperature gave the MeCN displaced products, [MI2(CO)3(4,4-bipy-N)2] (1) and (2). Equimolar amounts of [MI2(CO)3(NCMe)2] and L (L = PPh3, AsPh3 or SbPh3) react to give [MI2(CO)3(NCMe)L], which when reacted in situ with 4,4-bipy yield the new complexes, [MI2(CO)3(4,4-bipy-N)L] (3)–(8). Reaction of equimolar quantities of [WI2(CO)(NCMe)(
2-RC2R)2] (R = Me or Ph) and 4,4-bipy gave the new bis(alkyne) complexes, [WI2(CO)(4,4-bipy-N)(
2-RC2R)2] (9) and (10). Treatment of [MI2(CO)3(NCMe)2] with two equivalents of (9) or (10) in CH2Cl2 at room temperature affords the bimetallic complexes, [MI2(CO)3{WI2(CO)(4,4-bipy-N,N)(
2-RC2R)2}2] (11)–(14). Equimolar quantities of [MI2(CO)3(NCMe)(PPh3)] (prepared in situ) and (9) or (10), react to give the 4,4-bipy-bridged complexes, [MI2(CO)3{WI2(CO)(4,4-bipy-N,N)(
2-RC2R)2}(PPh3)] (15)–(18). All the new complexes, (1)–(18) were characterised by elemental analysis (C, H and N), i.r. and 1H-n.m.r. spectroscopy. 相似文献
2.
Adriano Duatti Simonetta Benetti Roberto Rossi Luciano Magon Ulderico Mazzi 《Transition Metal Chemistry》1981,6(6):380-381
Summary The reactions oftrans-ReOCl3(PPh3)2 with vinyl amides such as RCOCH=C(R)NH2, where R = CH2CH2CO2H and R = Ph and C6H13; or R = Me, CH2CH2CO2Me and R = Ph, give complexes of the type ReOCl2-[RC(O–)=CHC(R)=NH]PPh3, the coordination geometry of which have been deduced from i.r. and1H n.m.r. spectroscopic data. 相似文献
3.
New ruthenium(II) complexes, [Ru(CO)(B)(LL)(PPh3)] (where, LL = tridentate Schiff bases; B = PPh3, pyridine, piperidine or morpholine) have been prepared by reacting [RuHCl(CO)(PPh3)3] or [RuHCl(CO)(PPh3)2(B)] with Schiff bases containing donor groups (O, N, X) viz., salicylaldehyde thiosemicarbazone (X = S), salicylaldehyde semicarbazone (X = O), o-hydroxyacetophenone thiosemicarbazone (X = S) and o-hydroxyacetophenone semicarbazone (X = O). The new complexes were characterised by elemental analysis, spectral (i.r., 1H- and 31P-n.m.r.), data. 相似文献
4.
Paul K. Baker Kevin R. Flower Stephanie M. L. Thompson 《Transition Metal Chemistry》1987,12(4):349-351
Summary The seven-coordinate complexes [MI2(CO)3(NCMe)2] (M=Mo or W) react either in acetone or methanol with one equivalent of L (L=PPh3, AsPh3 or SbPh3) to give [MI2(CO)3(NCMe)L], which when reactedin situ with one equivalent of L {L=SC(NH2)2, SC(NMe2)2 or SC(NH2)Me} affords good yields of the new mixed complexes [MI2(CO)3LL]via successive displacement of acetonitrile ligands. 相似文献
5.
Marcelo O. Santiago Alzir A. Batista Marcio P. de Araújo Claudio L. Donnici Icaro de S. Moreira Eduardo E. Castellano Javier Ellena Sauli dos Santos Jr Salete L. Queiroz 《Transition Metal Chemistry》2005,30(2):170-175
A series of cis-{RuCl2(PPh3)2[4,4-(X)2-2,2-bipy]} [cis-chlorines; X=-H, -Me, -SMe, and (-Cl,-Me)] complexes have had their structures determined by single crystal X-ray diffraction. The geometry of these complexes, also determined in CH2Cl2 solution by 31P{1H}-n.m.r. spectroscopy, showed that the chemical shifts for the phosphorus atoms are slightly dependent on the pKa of the 4,4-(-X)2-2,2-bipy ligands. 相似文献
6.
Summary Rhodium(I) and iridium(I) mixed complexes of the formulae [M(diolefin)LL]ClO4, [M(diolefin)L2L]ClO4, [(diolefin)LIr(-L)2IrL(diolefin)](ClO4)2, [(diolefin)LM(-L-L)ML'(diolefin)](ClO4)2, [(diolefin)Rh{-(L-L)}2Rh(PPh3)2](ClO4)2 and [(diolefin)LIr{-(L-L)}2IrL (diolefin)](C1O4)2, (L=monodentate sulphur ligand, L-L=bidentate sulphur ligand, L=group Vb ligand; M=Rh, diolefin=1,5-cyclooctadiene (COD) or 2,5-norbornadiene (NBD); M=Ir, diolefin=COD) are described.Author to whom all correspondence should be directed. 相似文献
7.
von Niessen Wolfgang Cederbaum Lorenz S. Kraemer Wolfgang P. 《Theoretical chemistry accounts》1977,44(1):85-93
The vertical valence ionization potentials of cyclopropane, ethylene oxide and ethylene imine are calculated by a many-body Green's function method. For C3H6 the ordering of the ionization potentials is 2e(), 1e(), 2a1(), 1a2(), 1e(). The assignment of the 2a1 and the 1a2 ionization potentials which has been controversial is thus clarified. The ordering is in agreement with the result obtained via Koopmans' theorem. For ethylene oxide and ethylene imine Koopmans' theorem fails in predicting the correct order of ionic states. For C2H4O the ordering of the ionization potentials is 2b
1(), 4a
1, 1a
2(), 2b
2,3a
1, 1b
1(), 1b
2, 2a
1 and for C2H5N 6a, 5a, 3a, 2a, 4a, 3a, 1a, 2a. The agreement of the computed ionization potentials with the experimental values is very satisfactory. 相似文献
8.
Summary The platinum-platinum bonded [PtR2(OAc)L1]2 complexes (R = Ph, L1 = Et2S, n-Pr2S; R =p-tolyl, L1 = Et2S), have been prepared by oxidising [PrR2L1 ]2 with AgOAc or Tl(OAc)3. The sulphide ligand is replaced by weak ligands to give [PtR2(OAc)L2]2 (L2 = PhNH2, 4-picoline, CI–) whereas PEt3 or P(OMe)3 react to give Pt2R4(OAc)2(PR3)(R = Et, OMe). The methyl platinum analogues could also be prepared. Similar complexes Pt2Me4(O2CCF3)2L3 (L3 = Et2S1 4-picoline) were obtained by the reaction of Hg(O2CCF3)2 with [PtMe2(O2CCF3)L3]2.31p,1H and13C n.m.r. of the complexes are reported. 相似文献
9.
Ru(PPh3)3Cl2 reacts with N(1)-alkyl-2-(arylazo)imidazoles, p-RC6H4N=NC3H2N2X, [RaaiX, R = H(a), Me(b), Cl(c); X = Me(1), Et(2), Bz(3)] under refluxing conditions in EtOH to give [Ru(RaaiX)2(PPh3)2](ClO4)2 · H2O complexes (4–6). RaaiX is a bidentate chelator (N, N) with N(imidazole), N and N(azo), N donor centres. Three isomers are present in the mixture in which the pairs of PPh3, N and N occupy cis–cis–trans, cis–trans–cis and cis–cis–cis, positions respectively. The isomers were identified by 1H-n.m.r. spectra. Four signals are observed in the aliphatic zone for N(1)-X; two are of equal intensity at higher and the other two signals at lower in the ratio 1:0.3:0.2 suggesting the presence of cis–cis–cis, cis–trans–cis and cis–cis–trans-geometry. The complexes display the allowed t
2(Ru)
*(RaaiX) transition. Cyclic voltammetry indicates two consecutive RuIII/II couples along with azo reductions. 相似文献
10.
Summary Upon u.v. irradiation of [Fe(CO)4(PR
3
)] with HSiR3 (HSiR3 = HSiMePh2, PR3 = PPh3; HSiR3 = HSiMe2Cl, PR3 = PPh3 or PMe2Ph; HSiR3 = HSiMeCl2, PR3 = PPh3, PMePh2, PMe2Ph or PMe3; HSiR3 = HSiCl3, PR3 = PPh3, PMePh2, PMe2Ph, PMe3 or PBu
3
n
) the corresponding hydridosilyl complexes [Fe(CO)3H(PR3)SiR3] are formed. The complexes have themer configuration with acis disposition of the hydride and the silyl ligands. Prolonged irradiation with an excess of silane results in the formation of bis-silyl complexes [Fe(CO)3(PR3)(SiR3)2], if electron density at the metal is not too high. Thus, [Fe(CO)3H(PPh3)SiMePh2] and [Fe(CO)3-H(PMe2Ph)SiMe2Cl] can be obtained but not the corresponding bis-silyl complexes. Most bis-silyl complexes are obtained asmer-isomers with acis-arrangement of the silyl ligands. Only for [Fe(CO)3(PR3)(SiCl3)2] with small phosphine ligands (PR3 = PMe3 or PMe2Ph) is thefac-isomer formed.Part VII of this series, ref. (1). 相似文献
11.
Marcella Massacesi Giovanni Micera Liliana Strinna Erre Gerolamo Devoto Ermanno Barni 《Transition Metal Chemistry》1985,10(7):249-251
Summary Copper(II) complexes [CuLX2], where L = 2-(2-methyl-8-quinolyl)benzoxazole, 2-(2-methyl-8-quinolyl)benzimidazole or 2-(4-methyl-8-quinolyl)-benzimidazole and X = Cl or Br, have been synthesized and characterized by conductivity and magnetic measurements, i.r., electronic and e.s.r. spectra.The ligands always behave as bidentateN-donors giving rise to monomeric compounds withpseudo-tetrahedral coordination geometry. 相似文献
12.
Helmut Kacholdt Peer Berges Günter Klar Winfried Hinrichs 《Transition Metal Chemistry》1987,12(6):515-520
Summary The chalcogenanthrenes Vn2EE; 2, 3, 7, 8-tetramethoxythianthrene (E=E=S), 2, 3, 7, 8-tetramethoxydibenzothiaselenin (E=S, E=Se), and 2, 3, 7, 8-tetramethoxyselenanthrene (E=E=Se), react with [{ReBr(CO)3(THF)}2] and [{PtXMe3}4] (X=Cl or Br) to give the dinuclear complexes [(fac-L3M)2(-X)2 (-Vn2EE)] (M=Re, L=CO, X=Br; M=Pt, L=Me, X=Cl or Br) in which the chalcogenanthrenes reveal a hitherto unknown co-ordination mode as bridging ligands. Telluranthrene (Pn2 Te2), however, forms mononuclear complexes of compositionfac-[L3MX(Pn2Te2)] (M=Re, L=CO, X=Br; M=Pt, L=Me, X=Br) with a chelating chalcogenanthrene ligand. Whereas the rhenium compounds are not stable enough in solution to be studied by i.r. spectroscopy, the platinum compounds can be well characterised by their1H n.m.r. spectra. Furthermore, the results of a single-crystal structure determination of [Pt2Cl2Me6(Vn2Se2)] are reported. The Pt–Se distance of 259 pm indicates a relatively weak interaction between the chalcogenanthrene and the remaining dinuclear fragment of the molecule. 相似文献
13.
Giovanni Coni Marcella Massacesi Gustavo Ponticelli Giovanna Puggioni Costantino Putzolu 《Transition Metal Chemistry》1987,12(4):379-381
Summary Palladium(II) and platinum(II) complexes [MLX2], where L=2-(4-methyl-2-pyridyl)benzimidazole (mpbi), 2-(4-methyl-2-pyridyl)benzoxazole (mpbo), 2-(4-methyl-2-quinolyl)benzoxazole (mpbo), 2-(4-methyl-8-quinolyl)benzoxazole (mq'bo), X=Cl. Br, together with M(mqbo)2Br2 and Pt2(mpbt)Cl4, where mpbt=2-(4-methyl-2-pyridyl)benzthiazole, have been synthesized and characterized by conductivity and magnetic measurements as well as by i.r. and electronic spectra. The ligands are bidentate chelates through the pyridine or quinoline and isoxazole or imidazole nitrogen atoms. The [MLX2] derivatives arecis, square planar. 相似文献
14.
Krishna Chandra Satpathy Ashok Kumar Panda Rushabha Mishra Indumati Panda Aditya Prasad Chopdar 《Transition Metal Chemistry》1989,14(5):381-383
Summary Binuclear metal complexes of the type [M(HDDB)-(H2O)2]2: where HDDB=1-hydroxy-2,3-dimethyl-4-(3-methyl-4-amino-5-mercapto-1, 2, 4-triazole)-1,4-diaza-1, 3-butadiene and M=manganese(II), cobalt(II), nickel(II) and copper(II), have been prepared and characterised by elemental and thermal analyses, magnetic measurements, electronic and i.r. spectra. Octahedral geometry around the metal(II) ions is proposed and the crystal field parameters of the cobalt(II) and nickel(II) complexes are also calculated. Fungicidal screening of the complexes has been made aginstHelminthosporium oryzae andFusarium oxysporium. 相似文献
15.
V. A. Mamedov V. N. Valeeva L. A. Antokhina G. M. Doroshkina A. V. Chernova I. A. Nuretdinov 《Chemistry of Heterocyclic Compounds》1993,29(5):607-611
The methyl ester and N,N-diethylamide of 2-azido-5-phenyl-4-thiazolecarboxylic acid were obtained by the reaction of the corresponding 4-substituted 2-hydrazino-5-phenylthiazole with NaNO2 in acid media. IR and UV spectroscopy were used to show that the compounds synthesized retain azide form in both the crystalline state and in solution. The reaction of azides with dicarbonyl compounds gave derivatives of 2-[5-methyl-4-acetyl-or 2-[5-methyl-4-ethoxycarbonyl-1,2,3-triazol-1-yl]-5-phenylthiazole-4-carboxylic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 710–714, May, 1993. 相似文献
16.
Rauth Goutam Kumar Das Debasis Sinha Chittaranjan Bag Kanchan Mahapatra Ambikesh 《Transition Metal Chemistry》2002,27(6):639-645
The reaction of dichloro{1-methyl-2-(arylazo)imidazole}palladium(II), Pd(RaaiMe)Cl2 where RaaiMe = p-R–C6H4N=N–C3H2N2-1-Me; R = H(1), Me(2), Cl(3), with pyridine bases [RPY: R = H (a), 4-Me (b), 4-Cl (c), 2-Me (d), 2,6-Me2
(e), 2,4,6-Me3
(f)] has been studied spectrophotometrically in MeCN at 451 nm. The products (4) have been isolated and characterised as trans-Pd(RPy)2Cl2. The kinetics of the nucleophilic substitution has been examined under pseudo-first-order conditions at 298 K. A single phase reaction step has been observed for bases such as Hpy (a), 4-MePy (b) and 4-ClPy (c) and follows the rate law: rate = (a + k[RPy]2[Pd(RaaiMe)Cl2]). The bases 2-MePy (d), 2,6-Me2Py (e) and 2,4,6-Me3Py (f) exhibits a bi-phasic reaction and follows the rate laws: rate–1 = (a + k[RPy][Pd(RaaiMe)Cl2]) and rate–2 = (a + k[RPy][Pd(RaaiMe)-Cl2]), where k is the third-order rate constant; k is the second-order first phase rate constant, k is the second-order second phase rate constant and a/a/a correspond to the solvent dependent constant of the respective reaction path. The rate data supports a nucleophilic association path. External addition of Cl– (LiCl) suppresses the rate, which follows the order: k/k/k (3) > k/k,k (1) > k/k,k (2). The k values are linearly related to the Hammett constants. The 2-substituted pyridines (d–f) remarkably reduce the rate and show a bi-phasic reaction behaviour as compared with 4-Rpy (a–c). This is attributed to the steric effect that destabilises the transition state. The rate decreases with increasing steric crowding at the ortho-position and follows the order: (d) > (f) > (e). The 4-substituted pyridines control the rate via an inductive effect and follow the order: (b) > (a) > (c). 相似文献
17.
Gridchin S. N. Kochergina L. A. Pyreu D. F. Shmatko Yu. M. 《Russian Journal of Coordination Chemistry》2004,30(11):781-785
Stability constants of the manganese(II) complexes with 2-hydroxypropylene-1,3-diamine-N,N,N,N-tetraethanoic and ethylenediamine-N,N,N,N-tetraethanoic acids were determined by the potentiometric method at 298.15 K and ionic strengths of 0.1, 0.5 and 1.0 (KNO3). The data obtained were extrapolated to the zero ionic strength of the solution using the equation with one individual parameter. 相似文献
18.
Larry S. Gelfand Louis L. Pytlewski Chester M. Mikulski Anthony N. Speca Nicholas M. Karayannis 《Transition Metal Chemistry》1979,4(6):354-360
Summary During interaction of ethanol-triethyl orthoformate solutions of nicotinic or isonicotinic acidN-oxides (LH and LH, respectively) with MCl2 (M = Mn, Co, Ni), only one true adduct, of the Ni(LH)3Cl2 · 2 H2O type was obtained. In all other cases, partial substitution of Cl– ions with the corresponding pyridinecarboxylateN-oxide anionic ligands (L or L) occurred. As a result, mixed ligands (LH-L or LH-L) were precipitated, as follows: Mn(LH)2LCl, Co(LH)LCl, Mn(LH)LCl · 4H2O, Co(LH)LCl · H2O and Ni2(LH)LCl3 · 6 H2O. The insolubility of the new complexes in all common solvents, combined with the pronounced tendency of the 3- and 4-pyridinecarboxylates and theirN-oxides to function as bidentate bridging ligands, favours bi- or polynuclear structures. Spectral data suggest that Ni(LH)3Cl2 · 2 H2O is hexacoordinate, and the rest of the new complexes pentacoordinate. Bi- or polynuclear structures, involving double -M-(L)2-M- or-M-(LH)2-M- and single -M-(L)-M- or-M(L)-M-(LH)-M- bridges, were proposed on the basis of the overall evidence; additional features of the proposed structural types are: exclusively coordinated chloro ligands, in all cases; aqua ligands [Co(LH)LCl · H2O]; lattice water [Ni(LH)2Cl2 · 2H2O]; both lattice and coordinated H2O [Mn(LH)LCl · 4H2O, and Ni2(LH)LCl3 · 6H2O]; and, with the exception of Ni2(LH)LCl3 · 6 H2O, terminal, unidentate, N-O oxygen-bonded LH or LH ligands.Abstracted in part from the Ph.D. Thesis (in preparation) of L. S. Gelfand, Drexel University. 相似文献
19.
Bibasic tetradentateSchiff bases having the donor system OH–NX–NX–OH have been shown to form UO2(NO3)2(SBH2) type of derivatives [SBH2 is the molecule of the bibasic tetradentateSchiff bases such as HOC6H4C(R) N(CH2)
n
NC(R)C6H4OH (where R=H or CH3 andn=2 or 3) and HOC(R)CHC(CH3)N(CH2)
n
NC(CH3)CH C(R)OH (where R=CH3 or C6H5 andn=2 or 3)]. The 11 stoichiometry of these complexes is shown by elemental analysis and conductometric titrations. The molar conductence values in nitrobenzene indicate the non-electrolytic behaviour and the magnetic susceptibility measurements by the Gouy method show these complexes to be diamagnetic.With 1 Figure 相似文献
20.
Summary Complexes of NiII with isopropylxanthate and Lewis bases as mixed N-ligands of composition [Ni(i-prxa)2(L)] and [Ni(i-prxa)2(L)2] have been prepared, where i-prxa = i-C3H7OCS
2
-
, and L = ethylenediamine, 2,2-bipyridine, 1,10-phenanthroline or 5-nitro-1,10-phenanthroline, and L =-picoline or benzothiazole. On the basis of their chemical analyses, i.r. and electronic spectra, magnetic measurements, thermal analyses and molar conductivities, an octahedral structure is proposed. The crystal and molecular structures of [Ni(i-prxa)2(phen)] and [Ni(i-prxa)2(btz)2] were determined, showing oncis-octahedral andtrans-octahedral coordination spheres, respectively, with an NiS4N2 chromophore. 相似文献