共查询到20条相似文献,搜索用时 15 毫秒
1.
M. Fernanda N.N. Carvalho Armando J.L. Pombeiro 《Journal of organometallic chemistry》1991,410(3):347-355
Reaction of trans-[ReCl(CNR)(dppe)2] (R = Me (Ia) or tBu (Ib); DPPE = Ph2PCH2CH2PPh2) in CH2Cl2 with cynamide in the presence of TlBF4 forms the new cynamide-isocyanide complexes trans-[Re(CNR)(NCNH2)(dppe)2][BF4] (R = Me (IIa) or tBu (IIb)), which upon treatment by tBuOK or Et3N give trans-[Re(NCNH)(CNR)(dppe)2] (R = Me (IIIa) or tBu (IIIb)). The electrochemical behaviour of these species was studied by cyclic voltammetry and controlled potential electrolysis at a Pt electrode in an aprotic solvent, and cathodic reduction of II results in the formation of III. 相似文献
2.
II 《Journal of organometallic chemistry》1993,450(1-2):263-267
Treatment of [Pd{CH2C(CH3)CH2}(Ph2PPy)Cl] (Ph2PPy = 2-(diphenylphosphino)pyridine) with cis-[Pd(tBuNC)2Cl2] in dichloromethane affords the mixed isocyanide-tertiary phosphine complex cis-[Pd(tBuNC)Ph2PPy)Cl2], in which the Ph2PPy is a monodentate P-donor, and [{Pd[CH2C(CH3)CH2]Cl}2]. The steric effects of the Ph2PPy bridging ligand in determining the reaction course is discussed. The complex cis-[Pd(tBuNC)(Ph2PPy)Cl2] was crystallographically characterized: P21/n, a = 15.143(2), b = 9.527(1), c = 17.517(4) Å, β = 113.96(1)°, V= 2309.4(7) Å3, Z = 4. The final R value was 0.044, Rw= 0.046 for the 3078 reflections with I > 3σ(I). 相似文献
3.
Trans-dichlorobis(ethylenediamine) cobalt(III) terafluoroborate was synthesised and detailed packing analysis was undertaken to delineate the topological complimentarity of [trans-Co(en)2Cl2]+ and BF4− ions by second sphere coordination. The complex was completely characterised by elemental analyses, solubility product measurement and spectroscopic studies (IR, UV–Vis, multinuclear NMR). In the crystal lattice, discrete ions [trans-Co(en)2Cl2]+ and BF4− are arranged in A–B–A–B pattern (in both a and c directions of the lattice) forming columns of anions and cations. Crystal lattice is stabilized by electrostatic forces of attraction and hydrogen bonding interactions, i.e. N–HF− and N–HCl involving second sphere coordination. It appears that the topological features of [trans-Co(en)2Cl2]+ are conducive for generating second sphere interactions. This strategy may be used as a viable method for the capture of other fluoroanions. 相似文献
4.
M. T. Alonso O. Juanes J. de Mendoza J. C. Rodrí guez-Ubis 《Journal of organometallic chemistry》1992,430(3):335-347
Palladium(II) coordination complexes of nine 3- or 5-arylpyrazoles (phenyl, 2-bromophenyl, or 3-methoxyphenyl), as well as of 3,5-diphenylpyrazole, are reported. A cis-trans mixture of [PdL2Cl2] isomers is found in the case of 3-aryl-1-methylpyrazoles, the cis-isomers being transformed into trans by heating. Only trans isomers are isolated with the other ligands. Cyclopalladation of 3-ary]-1-methylpyrazoles can be performed with palladium(II) acetate, and the resultant μ-acetate bridged dimers can be transformed into μ-chloro bridged dimers or acetylacetonate monomers. The structures of the complexes have been characterized by 1H- and 13C-NMR spectroscopy. 相似文献
5.
The nucleophile [ArTe−] generated in situ borohydride solution of Ar2Te2, reacts with 2-(chloromethyl) tetrahydrofuran and 2-(2-bromoethyl)-1,3-dioxolane resulting in L1 and L2, respectively. The complexes of palladium(II) and platinum(II) with L1/L2 having stoichiometries [MCl2·L2], [ML2](ClO4)2, [(DPPE)ML2](ClO)4)2, [(PPh3)2ML2](ClO4)2 and [(phen)ML2](ClO4)2 (where L = L1/L2 DPPE = Ph2PC H2CH2PPh2, PHEN = 1,10-phenanthroline and M = Pd/Pt) have been synthesized. IR, 1H, 125Te{1H} and 31P{1H} NMR and UV-vis spectral data of these species in conjunction with their molar conductance and molecular weight data have been used to authenticate the new species. In all complexes (1–20) the ligands L1 and L2 are coordinated through tellurium and in the complexes of formula [ML2](ClO4)2 (M = Pd, Pt) the ligand is bidentate with the oxygen atom used in complexation. In solution, complexes PtCl2L2 exist as a mixture of cis and trans isomers whereas only the trans isomer was observed for the palladium analogues. The [(phen)PdL2](ClO4)2(Q) quenches 1O2 readily. The plot of log [Q] vs time is linear. Mechanism compatible with the experimental observations is proposed. 相似文献
6.
[Mo2(OAc)4] reacts with three or more equivalents of lithium chloride and PMe3 in thf to give [Mo2Cl3(μ-OAc)(PMe3)3]0.75thf (1). The IR spectrum of the complex shows Mo---O and Mo---Cl stretches at 350 and 300 cm−1 respectively and the 1H and 13C NMR spectra suggest several species are present in solution. [Mo2Cl3(μ-OAc)(PMe3)3] converts slowly in thf to [Mo2Cl4(PMe3)4] and [Mo2(OAc)4]. The structure of [Mo2Cl3(μ-OAc) (PMe3)3]0.5C6H5Me (2) has been determined by single-crystal X-ray diffraction methods. Crystals of the toluene solvate are tetragonal with a = 20.726(2), c = 11.776(2) Å, space GROUP = I4cm. The structure was solved by Patterson and Fourier methods and refined to R of 0.035 for the 539 observed data. The molecule contains two metal centres each of which shows 5-fold coordination. The two molybdenum atoms are linked by an acetate bridge and a short Mo---Mo bond of 2.121(3) Å. Remaining coordination sites are occupied on Mo(1) by two Cl and one PMe3 and on Mo(2) by one Cl and two PMe3 groups. 相似文献
7.
Yolanda Prieto Marcelo Muoz Vernica Arancibia Mauricio Valderrama Fernando J. Lahoz M. Luisa Martín 《Polyhedron》2007,26(18):5527-5532
The reaction of the dimer complex [{Ru(CO)3Cl2}2] with the ligands 4,6-dichloroquinoline-5,8-dione and 6-methoxybenzo[g]quinoline-5,10-dione in ethanol solution led to the neutral mononuclear complexes of general formula [Ru(CO)2Cl2(κ2-quinolinedione-N,O)]. The complexes were characterized by elemental analysis, IR and RMN spectroscopy, and the molecular structure of [Ru(CO)2Cl2(6-methoxybenzo[g]quinoline-5,10-dione)] was determined by single-crystal X-ray diffraction. The redox chemistry of ligands and complexes was investigated by cyclic voltammetry, and their potential antitumor activity was also evaluated. 相似文献
8.
翁维正 《高等学校化学学报》1994,15(2):173
采用NMR方法考察了室温和低温(-78~60℃)下Pd2X2(dpm)2(X=NCO-,CH3CO2-,SCN-和NO3-,dpm=Ph2PCH2PPh2)与H2S在CD2Cl2或CDCl3中的反应。结果表明,在X=NCO-和CH3CO2-的情况下,H2S优先与这些Pd配合物的阴离子作用生成相应的共轭酸HX和Pd2(SH)2(dpm)2,后者在H2S存在下又进一步转化为Pd2(SH)2(dpm)2(μ-S);当X=SCN-和NO3-时,反应则生成结构可能为[Pd2(H)(SH)(μ-SH)(dpm)2]+的双核Pd配合物。 相似文献
9.
The reaction of 2-(1-methyl-2-piperidinyl)ethanethiol with sodium tetrachloro-palladate(II) at pH = 8 yields a yellow precipitate of formula [Pd2(C8H16NS)2Cl2] which crystallized in the orthorhombic space group Pcab with a = 22.050(4) Å, b = 14.644(3) Å, c = 13.834(3) Å, V = 4467(3) Å3, and Z = 8. The organic ligands chelate to one Pd atom through the S and N atoms and bridges to another Pd atom through the S atom to form a dimer in which each molecule of the organic ligand has the same chirality. IR, UV—Vis and 1H NMR spectra are presented for this compound. 相似文献
10.
Guillermo Díaz 《Polyhedron》1988,7(24):2743-2752
An improved synthetic method has been found for the preparation of the pentamethylcyclopentadienyl rhenium dicarbonyldihalide complexes. From the reaction of (η5-C5Me5)Re(CO)3 with Br2 or I2 in THF-H2O a mixture of cis and trans isomers of (η5-C5Me5)Re(CO)2X2 X = Br and I is formed. On the other hand, the reaction of [(η5-C5Me5)Re(CO)3C1][SbC16] in water gives the cis-(η5-C5Me5)Re(CO)2C12 complex. The solid IR spectra of the dicarbonyldihalide complexes are recorded and an assignment of the normal modes in terms of local symmetry is suggested by comparison with those observed in analogous molecules. A normal coordinate analysis performed using a modified general valence force field and considering simplified models, confirms most of the experimental assignments. The set of valence force constants reflects the structure of the isomers under study. 相似文献
11.
Reaction of cis-[Ptph2(SMe2)2] with Me2PCH2PMe2 (dmpm) gave cis-[PtPh2(dmpm-P)2] (1) or cis,cis-[Pt2Ph4(μ-dmpm)2] (2) and reaction of 1 with [Pt2Me4(μ-SMe2)2] gave cis,cis-[Ph2Pt(μ-dmpm)2PtMe2] (3). Reaction of 1 with trans-[PtClR(SMe2)2] gave cis,trans-[Ph2Pt(μ-dmpm)2PtClR], R = Me (5) or Ph (6), and in polar solvents, these isomerized to give [Ph2Pt(μ-dmpm)2PtR]+Cl−. When R = Me, further isomerization via the phenyl group transfer gave [PhMePt(μ-dmpm)2PtPh]+Cl−. Oxidative addition of methyl iodide occurred reversibly at the cis-[PtMe2P2 unit of 3 to give cis,fac-[Ph2Pt(μ-dmpm)2PtIMe3] but complex 2 failed to react with MeI. A comparison with similar known complexes of Ph2PCH2PPh2 (dppm) is made and differences are attributed primarily to the lower steric hindrance of dmpm. 相似文献
12.
Kom-Bei Shiu Shin-Jay Yu Yu Wang Gene-Hsiang Lee 《Journal of organometallic chemistry》2002,650(1-2):37-42
Treatment of [Ru2(CO)4(MeCN)6][BF4]2 or [Ru2(CO)4(μ-O2CMe)2(MeCN)2] with uni-negative 1,1-dithiolate anions via potassium dimethyldithiocarbamate, sodium diethyldithiocarbamate, potassium tert-butylthioxanthate, and ammonium O,O′-diethylthiophosphate gives both monomeric and dimeric products of cis-[Ru(CO)2(η2-(SS))2] ((SS)−=Me2NCS2− (1), Et2NCS2− (2), tBuSCS2− (3), (EtO)2PS2− (4)) and [Ru(CO)(η2-(Me2NCS2))(μ,η2-Me2NCS2)]2 (5). The lightly stabilized MeCN ligands of [Ru2(CO)4(MeCN)6][BF4]2 are replaced more readily than the bound acetate ligands of [Ru2(CO)4(μ-O2CMe)2(MeCN)2] by thiolates to produce cis-[Ru(CO)2(η2-(SS))2] with less selectivity. Structures 1 and 5 were determined by X-ray crystallography. Although the two chelating dithiolates are cis to each other in 1, the dithiolates are trans to each other in each of the {Ru(CO)(η2-Me2NCS2)2} fragment of 5. The dimeric product 5 can be prepared alternatively from the decarbonylation reaction of 1 with a suitable amount of Me3NO in MeCN. However, the dimer [Ru(CO)(η2-Et2NCS2)(μ,η2-Et2NCS2)]2 (6), prepared from the reaction of 2 with Me3NO, has a structure different from 5. The spectral data of 6 probably indicate that the two chelating dithiolates are cis to each other in one {Ru(CO)(η2-Et2NCS2)2}fragment but trans in the other. Both 5 and 6 react readily at ambient temperature with benzyl isocyanide to yield cis-[Ru(CO)(CNCH2Ph)(η2-(SS))2] ((SS)=Me2NCS2− (7) and Et2NCS2− (8)). A dimerization pathway for cis-[Ru(CO)2(η2-(SS))2] via decabonylation and isomerization is proposed. 相似文献
13.
M. F tima C. Guedes da Silva Elsa M. P. R. P. Branco Yu Wang Jo o J. R. Fraú sto da Silva Armando J. L. Pombeiro Roberta Bertani Rino A. Michelin Mirto Mozzon Franco Benetollo Gabriella Bombieri 《Journal of organometallic chemistry》1995,490(1-2):89-99
Complexes trans-[PtX(L)(PPh3)2]A [1: X = CF3; A = BF4; L = NCNH2, NCNMe2, NCNEt2, or NCNC(NH2)2. 2: X = Cl; A = BPh4; L = NCNMe2 or NCNEt2] and cis-[PtCl(L)(PPh3)2][BPh4] [3: L = NCNH2 or NCNC(NH2)2], which appear to be the first cyanamide or cyanoguanidine complexes of platinum to be reported, have been prepared by treatment of trans-[PtBr(CF3)(PPh3)2] (in CH2Cl2/acetone and in the presence of Ag[BF4]) or of cis-[PtCl2(PPh3)2] (in THF and in the presence of Na[BPh4]), respectively, with the appropriate substrate. In KBr pellets or in solution 1 (L = NCNMe2 or NCNEt2) undergoes ready replacement of the organocyanamide (under the trans influence of CF3) by bromide to regenerate trans-(PtBr(CF3)(PPh3)2]. The X-ray structure of 1 (X = CF3, A = BF4, L = NCNEt2) is also reported, and shows the presence of two apical intramolecular contacts of the metal with two ortho-hydrogen atoms of the phosphines, whereas the amine N atom of the diethylcyanamide is trigonal planar in the linear NCN framework with a delocalized π system. 相似文献
14.
Howard C. Clark George Ferguson Vimal K. Jain Masood Parvez 《Journal of organometallic chemistry》1984,270(3):365-373
Compounds of the types Me3PtX(NN) (where X = Cl, I, OAc, NO3; NN = bis(1-pyrazolyl)methane (pz2CH2), bis(3,5-dimethyl-1-pyrazolyl)methane ((Me2pz)2CH2), or bis(2-pyridyl)methane (py2CH2)), [Me3Pt(NNN)][PF6] (where NNN=tris(1-pyrazolyl)methane (pz3CH), or tris(2-pyridyl)methane (py3CH)), and [Me3Pt((Me2pz)2CH2(py)][PF6] have been prepared and characterized by elemental analyses and 1H and 13C NMR spectroscopy; the structure of Me6PtI[(Me2pz)2CH2] (1) has also been determined by X-ray crystallography. Crystals of 1 are orthorhombic, space group Pcmn with four molecules in a unit cell of dimensions a 11.936(5), b 14.462(4), c 10.138(5) Å. The structure was solved by the heavy-atom method and refined by full-matrix least-squares calculations to R = 0.022 for 1719 observed data. The molecule has crystallographic mirror symmetry. The Pt atom has octahedral geometry with one methyl group trans to iodine and two methyl groups trans to the N atoms of the bidentate ligand (Pt---I 2.843(1), Pt---N, 2.236(4), Pt---C 2.077(6) (trans to I) and 2.032(5) Å (trans to N)). 相似文献
15.
The synthesis, characterization and thermal behaviour of 12 dinuclear, orthopalladated complexes derived from Schiff's bases are reported. The complexes are of the type [Pd2(H-X)2C6H3(OR)-C(Z) = N-C6H4R'2] (X = OAc, Cl, Br, SCN; Z = H, CH3; R' = OR, R; R = C10H21) and ten of them exhibit ordered mesophases (SC and SA). The molecules were characterized structurally by I.R. and 1H N.M.R. spectroscopy in order to elucidate the possible existence of isomers. The connection between their molecular structures and their mesogenic properties is discussed. 相似文献
16.
Norbornadiene undergoes [2 + 2] reaction in THF in the presence of NiX2 and zinc metal powder to give an exo-trans-exo dimer and an exo-trans-exo-trans-exo trimer. In these products, the norbornadiene molecules are linked to each other by forming cyclobutane rings with all cyclobutane carbons occupying exo positions relative to the bridging carbons on the two norbornadiene fragments. Polymerization of norbornadiene occurs if the catalyst NiX2 is replaced by Ni(PPh3)2Cl2. 1,4-Dihydro-1,4-epoxynaphthalene, 5,8-dimethoxy-1,4-dihydro-1,4-epoxynaphthalene, 5-methoxy-1,4-dihydro-1,4-epoxynaphathalene and methyl 1,4-dihydro-1,4-iminonaphthalene-9-carboxylate also dimerize to give exo-trans-exo products in excellent yields in toluene in the presence of Ni(PPh3)2Cl2 and Zn powder. For the dimerization products of 5-methoxy-1,4-dihydro-1–4-epoxynaphthalene, cis and trans isomers with respect to the orientation of methoxy groups in about 1 : 1 ratio were oberved. Under similar reaction conditions for the dimerization of norbornadiene, norbornene undergoes reductive dimerization to afford a product which consists of two norbornyl groups. The structure of this product is also exo-trans-exo. 相似文献
17.
Gianfranco Bellachioma Giuseppe Cardaci Alceo Macchioni Gustavo Reichenbach 《Journal of organometallic chemistry》1997,540(1-2):7-13
The equilibrium constants of the reaction of cis, trans-[Ru(CO)2(PMe3)2(CH3)I] (Mc) with carbon monoxide to give cis, trans[Ru(CO)2(PMe3)2 (COMe)i] (Ac) and trans, trans[Ru(CO)2(PMe3)2(COMe)I] (At) were measured at various temperatures in toluene. The thermodynamic parameters are compared with those obtained for the isoelectronic complexes of iron, and the trend is discussed. The kinetics of the carbonylation reaction of Mc, as well as those of the inverse decarbonylation reaction of At were measured. The kinetics of the carbonylation of the new complex trans, trans-[Ru(CO)2(PMe3)2(CH3)I] (Mt) were also investigated. All the results afford further support to the previously proposed CO insertion mechanism occurring via methyl migration. The comparison of these kinetic results with those of isoelectronic complexes of iron indicates that ruthenium is more reactive than iron, which is reflected by its greater aptitude to act as catalyst in many processes. 相似文献
18.
Kom-Bei Shiu Li-Yuan Yeh
Shie-Ming Peng
Ming-Chu Cheng 《Journal of organometallic chemistry》1993,460(2):203-211The neutral nitrogen-bidentate ligand, diphenylbis(3,5-dimethylpyrazol-1-yl)methane, Ph2CPz′2, can readily be obtained by the reaction of Ph2CCl2 with excess HPz′ in a mixed-solvent system of toluene and triethylamine. It reacts with [Mo(CO)6] in 1,2-dimethoxyethane to give the η2-arene complex, [Mo(Ph2CPz′2)(CO)3] (1). This η2-ligation appears to stabilize the coordination of Ph2CPz′ 2 in forming [Mo(Ph2CPz′2)(CO)2(N2C6H4NO2-p)][BPh4] (2) and [Mo(Ph2CPz′2)(CO)2(N2Ph)] [BF4] (3) from the reaction of 1 with the appropriate diazonium salt but the stabilization seems not strong enough when [Mo{P(OMe)3} 3(CO)3] is formed from the reaction of 1 with P(OMe)3. The solid-state structures of 1 and 3 have been determined by X-ray crystallography: 1-CH2Cl2, monoclinic, P21/n, a = 11.814(3), b = 11.7929(12), c = 19.46 0(6) Å, β = 95.605(24)°, V = 2698.2(11) Å3, Z = 4, Dcalc = 1.530 g/cm3 , R = 0.044, Rw = 0.036 based on 3218 reflections with I > 2σ(I); 2 (3)-1/2 hexane-1/2 CH3OH-1/2 H2O-1 CH2Cl2, monoclinic, C2/c, a = 41.766(10), b = 20.518(4), c = 16.784(3) Å, β = 101.871(18)°, V = 14076(5) Å3, Z = 8, Dcalc = 1.457 g/cm3, R = 0.064, Rw = 0.059 based on 5865 reflections with I > 2σ(I). Two independent cations were found in the asymmetric unit of the crystals of 3. The average distance between the Mo and the two η2-ligated carbon atoms is 2.574 Å in 1 and 2.581 and 2.608 Å in 3. The unfavourable disposition of the η2-phenyl group with respect to the metal centre in 3 and the rigidity of the η2-arene ligation excludes the possibility of any appreciable agostic C---H → Mo interaction. 相似文献
19.
Joseph P. Morrall Clem E. Powell Robert Stranger Marie P. Cifuentes Mark G. Humphrey Graham A. Heath 《Journal of organometallic chemistry》2003,670(1-2):248-255
The complexes trans-[Os(CCPh)Cl(dppe)2] (1), trans-[Os(4-CCC6H4CCPh)Cl(dppe)2] (2), and 1,3,5-{trans-[OsCl(dppe)2(4-CCC6H4CC)]}3C6H3 (3) have been prepared. Cyclic voltammetric studies reveal a quasi-reversible oxidation process for each complex at 0.36–0.39 V (with respect to the ferrocene/ferrocenium couple at 0.56 V), assigned to the OsII/III couple. In situ oxidation of 1–3 using an optically transparent thin-layer electrochemical (OTTLE) cell affords the UV–Vis–NIR spectra of the corresponding cationic complexes 1+–3+; a low-energy band is observed in the near-IR region (11 000–14 000 cm−1) in each case, in contrast to the neutral complexes 1–3 which are optically transparent below 20 000 cm−1. Density functional theory calculations on the model compounds trans-[Os(CCPh)Cl(PH3)4] and trans-[Os(4-CCC6H4CCPh)Cl(PH3)4] have been used to rationalize the observed optical spectra and suggest that the low-energy bands in the spectra of the cationic complexes can be assigned to transitions involving orbitals delocalized over the metal, chloro and alkynyl ligands. These intense bands have potential utility in switching nonlinear optical response, of interest in optical technology. 相似文献
20.
Subrata Maity Ramkrishna Roy Chittaranjan Sinha Wen-Jyh Sheen Kaliyamoorthy Panneerselvam Tian-Huey Lu 《Journal of organometallic chemistry》2002,650(1-2):202-209
Binuclear chloro-bridged cyclopalladated azobenzenes [Pd(A)Cl]2 (A=ortho-metallated azobenzene or its derivatives) have been reacted with aqueous (aq.) AgNO3 followed by the addition of 2-hydroxypyridine (2-PyOH; donor centres of deprotonated form abbreviated N,O)/2-mercaptopyridine (2-PySH; donor centres of deprotonated form abbreviated N,S) in presence of Et3N to synthesise bridged dinuclear compound [Pd(A)(μ-N,O)]2–[Pd(A)(μ-N,S)]2. The compositions of the complexes have been established by elemental analyses, IR, UV–vis, 1H and 13C-NMR spectral data. The structural confirmation has been carried out by X-ray crystallography. The structures show anti-symmetric metallacycle in the dimer and N,O/N,S bridging arrangement. The dimer [Pd(A1)(μ-N,X)]2 shows strong PdPd interaction (A1=2-(phenylazo)benzene). The coordination mode in [Pd(A1)(μ-N,O)]2 shows trans pyridine-N to Pd---N(azo) bond while in [Pd(A1)(μ-N,S)]2 pyridine-N is trans to the Pd---C bond. The square planes are convergent towards heterocyclic bridging side. 相似文献