共查询到20条相似文献,搜索用时 31 毫秒
1.
The new complexes trans-K[CrF(H2O)(en)2][Co(CN)6] aq. and trans- K[CrF(H2O)(tmd)2][Co(CN)6 aq. (en = ethylenediamine; tmd = 1,3 diaminepropane) have been prepared. The anation reactions have been studied with TG and DSC techniques. The anation reaction gives the new dinuclear species cis K[(aa′)2, FCr-NC-Co(CN)5] (aa′ = en.tmd). The reaction enthalpy of bridge formation has been determined. The activation energy has been calculated by non-isothermal methods. 相似文献
2.
《Journal of Inorganic and Nuclear Chemistry》1981,43(12):3113-3118
Dinuclear complexes with μ-cyano ligand of formula [(aa)2FCrNCM(CN)3] have been obtained by heating trans-[CrF(H2O)(aa)2][M(CN)4] (aa = ethylenediamine (en); 1,3-propanediamine (tmd); M Ni(II), Pd(II), Pt(II). Chemical analyses, conductivity measurements and electronic and IR spectra justify the formulation proposed. X-Ray diffraction indicates isomorphism for the three mixed complex salts of en, and for the tmd salts. The amine part of the en complexes undergoes a trans → cis change of configuration during the formation reaction; this change is not observed for the tmd complexes. The cis-bis (ethylenediamine) fluoro (tetracyanoplatinate(II)-N) Chromium(III): Cis-[(en)2FCrNCPt(CN)3] shows Pt-Pt interaction both in the solid state and in solution. 相似文献
3.
Summary Twelve dinuclear complexes, each with a bridging cyano group, of formulaecis-M[(aa)2FCr-NC-Cr(CN)5] andcis- M[(aa)2FCr-NC-CrNO(CN)4] (aa=ethylenediamine or 1,3-diaminopropane; M=K+, Na+ or NH
4
+
) have been prepared by solid state heating of the corresponding doubly complexed saltstrans-M[CrF(H2O)(aa)2][Cr(CN)6] andtrans-M [CrF(H2O)(aa)2][CrNO(CN)5]. All have been characterized by chemical analysis, electronic and i.r. spectra and conductivity measurements.Magnetic susceptibilities down to liquid helium temperature have been determined forcis-K[(en)2FCr-NC-Cr(CN)5],cis-K[(tn)2FCr-NC-Cr(CN)5] andcis-K[(en)2FCr-NC-CrNO-(CN)4]. Slight antiferromagnetic interactions have been found in the first two compounds (J=–1.4 and –1.2 cm–1, respectively). Thecis-K[(en)2FCr-NC-CrNO(CN)4] compound behaves as a Curie paramagnet and a structural model is proposed to explain this fact. 相似文献
4.
The solid phase thermal deaquation of trans[CrF(H2O)(aa′)2]K[Cr(CN)6]H2O and trans[CrF(H2O)(aa′)2]K[CrNO(CN)5]H2O (aa′=ethylenediamine or 1,3-diaminopropane) has been investigated by means of TG measurements. The kinetic parameters (activation energy, Ea, activation entropy, ΔS#, and frequency factor, k0) have been determined by comparison of the isothermal and non-isothermal studies for all the principal g(α) expressions. The values found for the activation energy are low (between 80 and 110 kJ mole?1, approximately) and permit the assignment of the deaquation-anation mechanism of the SN1 type, involving square-pyramid activated complex and elimination of water as Frenkel defects. 相似文献
5.
The (13)C chemical shifts of methylcobalt(III) compounds with saturated amine ligands in cis positions to the methyl group and a monodentate ligand, L = CN(-), NH(3), NO(2)(-), N(3)(-), H(2)O, or OH(-), in the trans position are reported. The amine ligands used, 1,2-ethanediamine (en), 1,3-propanediamine (tn), N,N'-bis(2-aminoethyl)-1,3-propanediamine (2,3,2-tet), N,N'-bis(3-aminopropyl)-1,2-ethanediamine (3,2,3-tet), and 1,4,8,11-tetraazacyclotetradecane (cyclam), all exert an apparent cis influence on the (13)C resonance signal of the coordinated methyl group. In the trans-[Co(en)(2)(CH(3))(L)](n+) series the (15)N resonance frequency of the coordinated en has also been measured. The influence of L on the en (15)N chemical shifts is reverse the influence on the methyl (13)C chemical shifts except in the case of L = NO(2)(-), which affects a further deshielding of the amine nitrogen nucleus. The methyl (1)J(CH) coupling constants in the trans-[Co(en)(2)(CH(3))(L)](n+) series range from 128.09 Hz (L = CN(-)) to 134.11 Hz (L = H(2)O). The crystal structures of trans-[Co(en)(2)(CH(3))(ClZnCl(3))], trans-[Co(3,2,3-tet)(CH(3))(N(3))]ClO(4), trans,trans-[(CH(3))(en)(2)Co(CN)Co(en)(2)(CH(3))](PF(6))(3)(CH(3)CN), and cis-[Co(en)(2)(CH(3))(NH(3))]ZnCl(4) were determined from low-temperature X-ray diffraction data. 相似文献
6.
Heteronuclear Coordination Compounds with Metal—Metal Bonds. VIII. New Heterodinuclear Complexes with Bonds between Copper(I) and Manganese(?I), Iron(?I), or Cobalt(?I) [(en)Cu? Mn(CO)5] ( 1a ), [(dien)Cu? Mn(CO)5] ( 1b ), [(en)Cu? Fe(CO)3(NO)] ( 2a ), [(dien)Cu? Fe(CO)3(NO)] ( 2b ), [(en)Cu? Co(CO)4] ( 3a ), and [(dien)Cu? Co(CO)4] ( 3b ) are new heterobinuclear metal—metal bonded complexes. The geometry of the [Mn(CO)5]?, [Fe(CO)3(NO)]?, and [Co(CO)4]? ions is distorted only to a less extend in accord with a heteropolar bond to copper. 相似文献
7.
The anation and decomposition reaction of trans[CrF(H2O)(aa′)2]S2O6 [aa′ = ethylenediamine (en); 1,3-diaminepropane (tmd)] have been studied by means of ATD, TG and DSC techniques. The first and only perfectly defined step is the anation reaction forming the species cis[CrF(S2O6)(aa′)2]. By means of DSC techniques, the enthalpies of reaction and the activation energies of both reactions have been estimated. The electronic spectra of the resultant products suggest cis configuration. A second step, preceding total decomposition of the complex, involves cis[CrF(S2O6)(aa′)2] → cis[CrF(SO4)(aa′)2] + SO2 which is contaminated by decomposition reactions. 相似文献
8.
Pritha Talukder Shyamapada Shit Heinrich N?th Matthias Westerhausen Alexander Nikolai Kneifel Samiran Mitra 《Transition Metal Chemistry》2012,37(1):71-77
A heterobimetallic cyano-bridged 1D coordination polymer of the composition [Ni(baepn)(μ-NC)Fe(CN)3(NO)(μ-CN)]n·3H2O has been synthesized by the reaction of nickel(II) nitrate hexahydrate, baepn (baepn = N, N′-bis(2-aminoethyl)-1,3-propanediamine), and sodium nitroprusside dihydrate in a methanol–water mixture. The complex was characterized
by physicochemical and spectroscopic methods. The crystal structure was established by single-crystal X-ray diffraction analysis.
It reveals cyano-bridged heterometallic chains consisting of alternating arrays of Ni(II) and Fe(II) atoms, both being embedded
in distorted octahedral environments. Low-temperature susceptibility measurements show the presence of weak antiferromagnetic
exchange interactions between paramagnetic Ni(II) centers (J = −0.46 cm−1) through long diamagnetic [Fe(CN)5(NO)]2− bridges. Spin state of the iron atom was established by 57Fe M?ssbauer spectroscopy. 相似文献
9.
Preparation and Properties of Vanadyl(IV) Pentacyanonitrosylferrate(II), VO[Fe(CN)5NO] · 2 H2O The preparation of VO[Fe(CN)5NO] · 2 H2O is described for the first time. Its electronic, infrared, and 57Fe-Mössbauer spectra were recorded and discussed. The thermal degradation was investigated by means of TG and DTA measurements and shows a very complex behaviour. A new preparative method for (VO)2[Fe(CN)6] · 10 H2O is also described and some of its spectroscopic properties were investigated and compared with those of VO[Fe(CN)5NO] · 2 H2O. 相似文献
10.
A series of new coordination polymers bearing the [B(O–C6H4–CN)4]– anion was synthesized. Two new, one dimensional coordination frameworks of the type M[B(O–C6H4–CN)4] (M = Ag, Cu) were obtained by salt metathesis. The reactivity towards organic Lewis‐bases was studied. The reaction with bidentate ligands yielded two dimensional networks with the general formula [M(L)][B(O–C6H4–CN)4] {L = 2,2′‐bipyridine, 4,4′‐bipyridine, 1,2‐bis(pyridyl)ethane, 1,4‐diazabicyclo[2.2.2]octane}. The synthesis, properties and single crystal structure are reported. 相似文献
11.
Mechanistic Insight into the Nitric Oxide Dioxygenation Reaction of Nonheme Iron(III)–Superoxo and Manganese(IV)–Peroxo Complexes
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Seungwoo Hong Dr. Pankaj Kumar Dr. Kyung‐Bin Cho Dr. Yong‐Min Lee Prof. Dr. Kenneth D. Karlin Prof. Dr. Wonwoo Nam 《Angewandte Chemie (International ed. in English)》2016,55(40):12403-12407
Reactions of nonheme FeIII–superoxo and MnIV–peroxo complexes bearing a common tetraamido macrocyclic ligand (TAML), namely [(TAML)FeIII(O2)]2? and [(TAML)MnIV(O2)]2?, with nitric oxide (NO) afford the FeIII–NO3 complex [(TAML)FeIII(NO3)]2? and the MnV–oxo complex [(TAML)MnV(O)]? plus NO2?, respectively. Mechanistic studies, including density functional theory (DFT) calculations, reveal that MIII–peroxynitrite (M=Fe and Mn) species, generated in the reactions of [(TAML)FeIII(O2)]2? and [(TAML)MnIV(O2)]2? with NO, are converted into MIV(O) and .NO2 species through O?O bond homolysis of the peroxynitrite ligand. Then, a rebound of FeIV(O) with .NO2 affords [(TAML)FeIII(NO3)]2?, whereas electron transfer from MnIV(O) to .NO2 yields [(TAML)MnV(O)]? plus NO2?. 相似文献
12.
IntroductionSince 184 8,whenPlayfairpublishedthefirstpaperrelatedtonitroprussides ,1thetransitionmetalpenta cyanonitrosylmetallatehydrateshavebeenwidelystudiedbecauseoftheirimportantrolesinmolecularsieves ,cationexchangers,electronscavengersandradionuclidesor bents .2 4 Thenitroprussides ,regardlessofthecationicmetal,arecurrentlyemployedasreversibleinhibitorsofagroupofenzymesknownassuperoxidedismutases .5Recently ,using [Fe(CN ) 5(NO) ]2 - asabuildingblock ,somenitroprusside bridgedpolymeri… 相似文献
13.
G. V. Markin Yu. A. Shevelev G. A. Domrachev G. K. Fukin E. V. Baranov M. A. Lopatin V. A. Kuropatov A. I. Kirillov A. S. Shavyrin Yu. A. Kurskii 《Russian Chemical Bulletin》2008,57(9):1970-1974
Radical-ion salts bis(biphenyl)chromium(i) 1,4-di(2-cyanoisopropyl)-1,4-dihydrofulleride [(Ph2)2Cr]+·[1,4-(CMe2CN)2C60]−· and bis(biphenyl)chromium(i) 1-(2-cyanoisopropyl)-1,2-dihydrofulleride [(Ph2)2Cr]+·[1,2-(CMe2CN)(H)C60]−·, the salt bis(biphenyl)chromium(i) (2-cyanoisopropyl)fulleride [(Ph2)2Cr]+·[(CMe2CN)C60]−, and neutral 1-(2-cyanoisopropyl)-1,2-dihydrofullerene 1,2-(CMe2CN)(H)C60 have been synthesized for the first time. The compounds [(Ph2)2Cr]+·[1,4-(CMe2CN)2C60]−· and [(Ph2)2Cr]+·[1,2-(CMe2CN)(H)C60]−· decompose in THF to form [(Ph2)2Cr]+·[(CMe2CN)C60]−, whose protonation affords 1,2-(CMe2CN)(H)C60. 1,4-Di(2-cyanoisopropyl)-1,4-dihydrofullerene 1,4-(CMe2CN)2C60 and 1,2-(CMe2CN)(H)C60 are stable in vacuo up to 513 K.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1935–1939, September, 2008. 相似文献
14.
Three new binuclear complexes: [(NO)(CN)4FeCN–Co(en)2] · H2O (1), [(NO)(CN)4FeCN–Co(pn)2] · 2H2O (2), and [(NO)(CN)4FeCN–Co(tn)2] · 3H2O (3) (en = ethylenediamine, pn = 1,2-diaminopropane; tn = 1,3-diaminopropane) have been prepared and their properties studies by i.r., u.v. spectroscopy, cyclic voltammetry, and by magnetic measurements. 相似文献
15.
Jaume Casabó Andreu Solans Carmen Diaz Joan Ribas Alexandre Seguí Montserrat Corbella 《Transition Metal Chemistry》1985,10(4):128-130
Summary Mixed difluoro(diamine)(diamme)chromium(III) complexes have been synthesized with ethylenediamine (en), 1,3 propanediamine(tn) and 1,2-cyclohexanediamine(chxn):trans-[CrF2(aa)(bb)]Br (aa=en, bb=tn; aa=tn, bb= chxn) andcis-[CrF2(aa)(bb)]Br (aa=en, bb=chxn). The corresponding fluoroaqua(diamine) (diamine)chromium(III) complexes have been prepared by acid hydrolysis as perchlorate or iodide salts. All have been characterized by chemical analysis, electronic and i.r. spectra and conductivity measurements. 相似文献
16.
Subratanath Koner Ashutosh Ghosh Nirmalendu Ray Chaudhuri 《Transition Metal Chemistry》1991,16(4):397-399
Summary Thermal reactions of [Ni(diamine)2(H2O)2](NO3)2 and [Ni(diamine)2(NO3)2] (where diamine=1,2-ethanediamine,N-methyl-1,2-ethanediamine,N-ethyl-1,2-ethanediamine, 1,3-propanediamine andN-methyl-1,3-propanediamine) have been investigated in the solid phase. The 1,2-ethanediamine andN-methyl-1,2-ethanediamine complexes undergo thermally induced endothermic irreversible isomeric transformations. In the 1,2-ethanediamine complex the transformation is thermochromic, whereas it is not for theN-methyl-1,2-ethanediamine complex. The transformations are explained in terms of the axial interaction of NO3 ions with nickel as well as to ligand field weakening resulting from conformational changes of the individual diamine chelate rings.Supplememtary data available: X-ray powder diffraction data (Table3). 相似文献
17.
Stefan Schaub Andreas Miska Dr. Jonathan Becker Dr. Stefan Zahn Prof. Dr. Doreen Mollenhauer Dr. Sadashivaiah Sakshath Prof. Dr. Volker Schünemann Prof. Dr. Siegfried Schindler 《Angewandte Chemie (International ed. in English)》2018,57(19):5355-5358
The iron(IV) oxido complex [(tmc)Fe=O(OTf)]OTf with the macrocyclic ligand 1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclo‐tetradecane (tmc) has been synthesized using ozone as an oxidant. By adding water to this compound the complex [(H2O)(tmc)Fe=O)](OTf)2 could be prepared. This complex is important in regard to a better understanding of the reactivity of FeIV oxido complexes. Mössbauer measurements using the solid compound showed an isomer shift of δ=0.19 mm s?1 and a quadrupole splitting ΔEQ=1.38 mm s?1, confirming the high‐valent FeIV state. DFT calculations were performed and led to an assignment of triplet spin multiplicity. Crystallographic characterization of [(H2O)(tmc)Fe=O)](OTf)2 as well as of starting materials [(tmc)Fe(CH3CN)](OTf)2 and [(tmc)Fe(OTf)]OTf together with previous results strongly suggest that [(H2O)(tmc)Fe=O)](OTf)2 was formed similar to the oxido–hydroxido tautomerism analogous to heme systems. 相似文献
18.
Characterization of Distortional Isomers of the Anions Pentacyano-oxo-molybdate(IV) and of Tetracyano-aqua-oxo-molybdate(IV) in the Solid State. Crystal Structures of [(C6H5)4P]3[MoO(CN)5] · 7 H2O (green), [(C6H5)4As]2[MoO(OH2)(CN)4] · 4 H2O (blue), and [(C6H5)4P]2[MoO(OH2) (CN)4] · 4 H2O (green) Preparation of a series of salts containing the new pentacyano-oxo-molybdate(IV) anion is described: Cs2H[MoO(CN)5] (blue), [(CH3)4N]2H[MoO(CN)5] · 2 H2O (blue) and [Cr(en)3] [MoO(CN)5] · 4 H2O (green). The green [(C6H5)4P]3[MoO(CN)5] · 7 H2O crystallizes triclinic in the space group P1 . The molybdenum(IV) center is in an pseudo-octahedral environment of a terminal oxo-group (d(Mo?O); 1.705(4) Å), a CN? group in the trans-position (d(Mo? C): 2.373(6) Å), and four equatorial CN? groups (averaged d(Mo? C): 2.178 (Å). The blue and green salts exhibit v(Mo?O) stretching frequencies at 948 cm?1 and 920 cm?1, respectively. Blue and green salts containing the [MoO(OH2)(CN)4]2? anion and [(C6H5)4P]+ or [(C6H5)4As]+ cations have been prepared and characterized by single crystal crystallography. [(C6H5)4P]2[MoO(OH2)(CN)4] · 4 H2O (green) and [(C6H5)4As]2[MoO(OH2)(CN)4] · 4 H2O (blue) crystallize monoclinic in the space group C—P21/n. They are considered to be distortional isomers of the complex anion: the green species has a Mo?O bond distance of 1.72(2) Å whereas for the blue species d(Mo?O) = 1.60(2) Å is found; the corresponding v(Mo?O) frequencies are at 920 cm?1 and 980 cm?1. 相似文献
19.
María M. Gutiérrez Alejandra E. Almaraz Sara E. Bari 《Journal of Coordination Chemistry》2015,68(17-18):3236-3246
The hydroxamic acids (RC(O)NHOH, HA) exhibit diverse biological activity, including hypotensive properties associated with formation of nitroxyl (HNO) or nitric oxide (NO). Oxidation of two HAs, benzohydroxamic and acetohydroxamic acids (BHA, AHA) by [Fe(CN)5NH3]2? or [Fe(CN)6]3? was analyzed by spectroscopic, mass spectrometric techniques, and flow EPR measurements. Mixing BHA with both Fe(III) reactants at pH 11 allowed detecting the hydroxamate radical, (C6H5)C(O)NO˙?, as a one-electron oxidation product, as well as N2O as a final product. Successive UV–vis spectra of mixtures containing [Fe(CN)5NH3]2? (though not [Fe(CN)6]3?) at pH 11 and 7 revealed an intermediate acylnitroso-complex, [Fe(CN)5NOC(O)(C6H5)]3? (λmax, 465 nm, very stable at pH 7), formed through ligand interchange in the initially formed reduction product, [Fe(CN)5NH3]3?, and characterized by FTIR spectra through the stretching vibrations ν(CN), ν(CO), and ν(NO). Free acylnitroso derivatives, formed by alternative reaction paths of the hydroxamate radicals, hydrolyze forming RC(O)OH and HNO, postulated as precursor of N2O. Minor quantities of NO are formed only with an excess of oxidant. The intermediacy of HNO was confirmed through its identification as [Fe(CN)5(HNO)]3? (λmax, 445 nm) as a result of hydrolysis of [Fe(CN)5(NOC(O)(C6H5)]3? at pH 11. The results demonstrate that hydroxamic acids behave predominantly as HNO donors. 相似文献
20.
《Journal of Coordination Chemistry》2012,65(3-4):343-353
Abstract A series of complexes of formula [(NC)5FeII—NC—FeII(CN)4L]n?, with L = H2O, pyridine, isonicotinamide and 4-cyanopyridine were prepared in aqueous solution by substitution of the corresponding [FeII(CN)5L]n? ions into [FeII(CN)5H2O]3?. The mixed valent (II, III) and fully oxidized (III, III) complexes were also obtained. The (II, II) complexes were moderately stable toward dissociation into the mononuclear species, but the mixed-valent ions were properly characterized by UV-vis-NIR spectroscopy and electrochemistry. Distinctive intervalence (IV) bands were assigned in the NIR region, with the energy being dependent on the binding properties of L; the IV band energy also correlated with the redox potential at the [NC—Fe(CN)4L] fragment. By application of the Hush model, a valence-trapped situation was found for the [(NC)5FeIII—NC—FeII(CN)4L]n? ions. The class II behavior shows, however, a value of H ab, the electronic coupling factor, of ca. 1600cm?1, indicating a moderate-to-strong communication between the metal centers. 相似文献