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171.
The gas-phase electronic absorption spectra of (6-C6R6)2Cr (R = Me (1) and Et (2)) reveal Rydberg structures, which disappear on going to the condensed phase. Each spectrum shows a Rydberg series converging to the ionization threshold. The first ionization potential determined as the series convergence limit is 4.662±0.008 eV for 1 and 4.667±0.019 eV for 2. The Rydberg bands are due to the transitions from the non-bonding MO 3dz2 to the R4s and Rnp (n = 4—10) levels. The influence of methyl and ethyl substituents on the term values of the Rydberg transitions depends on the principal quantum number of the Rydberg MO. 相似文献
172.
Summary Complexation equilibria of the Tl(I) ion with 18-crown-6 and dibenzo-18-crown-6 were studied polarographically in 10 nonaqueous solvents. The stability of the complexes is strongly influenced by the nature of solvents and varies with their Lewis basicities. It has been found that the logK
s value (K
s is the stability constant of the complex) can be well described by empirical relation logK
s=a DN+b, whereDN stands for the Gutmann donor number anda andb mark the regression coefficient. Addition of the second explanatory parameter, the acceptor number, is not statistically significant. This result is in agreement with the predominant role of Tl(I) ion solvation.
Elektrochemische Untersuchungen von Tl(I)-Kronenetherkomplexen in nichtwäßrigen Medien
Zusammenfassung Es wurden die Komplexierungsgleichgewichte des Tl(I)-Ions mit 18-Krone-6 und Dibenzo-18-krone-6 polarographisch in 10 nichtwäßrigen Lösungsmitteln untersucht. Die Stabilität der Komplexe wird sehr stark vom Solvens beeinflußt, wobei eine starke Abhängigkeit von der Lewis-Basizität beobachtet wird. Es wurde festgestellt, daß die logK s-Werte (K s ist die Komplexstabilitätskonstante) gut mit der empirischen Beziehung logK s=a DN+b beschrieben werden können, wobeiDN die Gutmann'sche Donorzahl unda undb die Regressionskonstanten bedeuten. Hinzunahme der Akzeptorzahl als zweiten Parameter bleibt statistisch insignifikant. Dieses Ergebnis stimmt mit dem dominierenden Einfluß der Tl(I)-Ionensolvatation überein.相似文献
173.
The overall stability constantsK
1 andK
2 of NdNO
3
2+
and Nd(NO3)
2
+
complexes were determined (K
1=1.77;K
2=1.28) using an extraction method with tri-n-butyl phosphate as the extractant. The ratio 1/2 of the stepwise stability constants is discussed. It was established that the Nd(NO3)
2
+
complex was an outer-sphere ion pair.
Die Assoziation von Nitrat-Ion mit Nd3+
Zusammenfassung Mittels einer Extraktionsmethode wurden die StabilitätskonstantenK 1 undK 2 von NdNO 3 2+ - und Nd(NO3)+-Komplexen bestimmt (K 1=1.77;K 2=1.28; Tri-n-butylphosphat als Extraktionsmittel). Das Verhältnis 1/2 der stufenweisen Stabilitätskonstanten wird diskutiert. Es stellte sich heraus, daß der Nd(NO3)+-Komplex als ein Outer-Shere-Ionenpaar vorliegt.相似文献
174.
V. S. Bogdanov S. V. Baranin A. Dib I. P. Yakovlev V. A. Dorokhov 《Russian Chemical Bulletin》1992,41(9):1693-1699
Mono- and binuclear boron chelates have been synthesized by the action of butylthiodibutylborane on the ethyl esters of 4-[N-(R-pyrid-2-yl)carbamoyl]-3-amino-2-cyanobuten-2-ic acids (codimers of N-(R-pyrid-2-yl) amides and the ethyl ester of cyanoacetic acid). Complexes of this type can exist in solution in the form of two tautomers: acetamide acid derivatives or the corresponding ketene N,O-acetals.N. D. Zelinski Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2162–2170, September, 1992. 相似文献
175.
Eva BeckerChristian Slugovc Eva RübaChristina Standfest-Hauser Kurt MereiterRoland Schmid Karl Kirchner 《Journal of organometallic chemistry》2002,649(1):55-63
The synthesis and some reactions of the Ru(II) and Ru(IV) half-sandwich complexes [RuCp(EPh3)(CH3CN)2]+ (E=P, As, Sb, Bi) and [RuCp(EPh3)(η3-C3H5)Br]+ have been investigated. The chemistry of this class of compounds is characterized by a competitive coordination of EPh3 either via a RuE or a η6-arene bond, where the latter is favored when the former is weaker, that is in going down the series. Thus in the case of Bi, the starting material [RuCp(CH3CN)3]+ does not react with BiPh3 to give [RuCp(BiPh3)(CH3CN)2]+ but instead gives only the η6-arene species [RuCp(η6-PhBiPh2)]+ and [(RuCp)2(μ-η6,η6-Ph2BiPh)]2+. Similarly, the EPh3 ligand can be replaced by an aromatic solvent or an arene substrate. Thus, the catalytic performance of [RuCp(EPh3)(CH3CN)2]+ for the isomerization of allyl-phenyl ethers to the corresponding 1-propenyl ethers is best with E=P, while the conversion drops significantly using the As and Sb derivatives. By the same token, only [RuCp(PPh3)(CH3CN)2]+ is stable in a non-aromatic solvent, whereas both [RuCp(AsPh3)(CH3CN)2]+ and [RuCp(SbPh3)(CH3CN)2]+ rearrange upon warming to [RuCp(η6-PhEPh2)]+ and related compounds. In addition, the potential of [RuCp(EPh3)(CH3CN)2]+ as precatalysts for the transfer hydrogenation of acetophenone and cyclohexanone has been investigated. Again aromatic substrates are clearly less suited than non-aromatic ones due to facile η6-arene coordination leading to catalyst's deactivation. 相似文献
176.
Inorganic ion-exchangers with a layered structure such as γ-zirconium and γ-titanium phosphates, intercalated with organic
diamines, are able to exchange Pt2+ ions to give new intercalation compounds that can be utilized in heterogeneous catalysis. The experiments performed at different
temperatures (25 and 45°C), show different ion uptakes, greater at 45°C and for the materials derived from γ-zirconium phosphate.
After platinum exchange, all the materials show an amorphization in the XRD if compared with their precursors. The thermal
behaviour of the platinum materials is specific, depending on the exchanger used and the ligand inside the exchanger. Pt2+ ion has a catalytic effect on ligand elimination in the γ-zirconium phosphate platinum compounds, but not in those derived
from γ-titanium. All the obtained yellow materials show a small step in the TG curves and simultaneously we have the Pt2+→Pt0 reduction: this is confirmed by XRD registered at the temperatures of the thermal effect, showing peaks at dhkl=2.27 and 1.95 Å.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
177.
In this paper some synthetic procedures to obtain (η6-arene)metal derivatives are reviewed. The metal-atom-arene-vapor co-condensation technique is the most appropriate to generate complexes of polycyclic aromatic hydrocarbons or heterocycles. As far as the aluminium halide-mediated synthesis is concerned, two classes of reaction are observed. When AlX3 is used with a metal halide in the presence of an aromatic hydrocarbon in the absence of any reducing agent, AlX3 can function as a dehalogenating agent, to give ionic compounds of general formula [M(η6-arene)n](AlX4)m, or it can add across the M---X bond with formation of M(μ-X)nAlX4−n systems. In both cases the metal displays its typical oxidation state. However, the use of AlX3 in combination with aluminium (the Fischer-Hafner reducing system) affords ionic or covalent low-oxidation-state metal(η6-arene) complexes. Attention is focused on our most recent results concerning the synthesis, properties and reactivity of η6-arene derivatives of Group 4 and 5 elements, showing, inter alia, the first example of a tetraarylborate anion behaving as a 12-electron donor to one metal atom and low-valent η6-arene compounds as useful reagents in the inorganic and coordination chemistry of the corresponding metal in nonaqueous systems. 相似文献
178.
Bossée A Afonso C Fournier F Tasseau O Pepe C Bellier B Tabet JC 《Journal of mass spectrometry : JMS》2004,39(8):903-912
Peptide metallation with Cu2+ was explored in the negative ESI mode using an ion trap mass spectrometer. Under these conditions, the [(M-3H) + CuII]- species formed were investigated under low-energy collision-induced dissociation conditions. MS2 experiments indicate a very different behavior of CuII metallated complexes compared with [M-H]- species. CuII induces an easy loss of CO2 and specific side-chain cleavages (by radical losses) at the C-terminal residue, as observed previously by prompt 'in source' dissociation experiments. The loss of CO2 yields an unstable carbylide that leads to further dissociations involving the migration of a proton or a hydrogen radical (through the reduction of CuII). Multistage MS3 experiments were carried out to rationalize this behavior. Fragmentation pathways are proposed in order to explain the product ions observed. The side-chain radical loss at the C-terminus was demonstrated to be a consecutive process. Finally, evidence is provided that the specific side-chain cleavages can be used for the differentiation of Leu/Ile and Gln/Lys residues when they are located at the C-terminus. The existence of a zwitterionic form in the case of the anionic YGGFK-CuII complex is proposed. 相似文献
179.
The use of sulfur-coordinating chiral ligands in the palladium-catalyzed asymmetric Tsuji—Trost reaction is reviewed. 相似文献
180.
一维链状冠醚配合物:[{Na(18-C-6)}2(H2O)]n[M(SCN)4]n(M=Pd、Pt)的合成与结构 总被引:1,自引:0,他引:1
The reactions of 18-crown-6 with Na2[M(SCN)4] (M= Pd,Pt) were studied and the complex 1 [{Na(18-C-6)}2(H2O)]n[Pd(SCN)4]n and complex 2 [{Na(18-C-6)}2(H2O)]n[Pt(SCN)4]n were characterized by ele-mental analysis, IR and X-ray diffraction analysis. The complexes belong to monoclinic, space group P21/n with cell dimensions, 1:a=1.05734(7),b=1.42250(10),c=1.47762(10) nm,β=107.5330(10)°,V=2.1192(2)nm3,Z=2,Dcalcd=1.460g·cm-3,F(000)=964,R1=0.0406,wR2=0.1264 and 2:a=1.05985(19),b=1.4237(3),c=1.4744(3) nm,β=107. 096(3)°, V=2.1264(7)nm3,Z=2,Dcalcd=1.690g·cm-3,F(000)=1028,R1=0.0292,wR2=0.0859. In the solid state, the complexes 1 and 2 show an one-dimensional chain of [{Na(18-C-6)}2(H2O)]2+ complex cations and [M(SCN)4]2- (M=Pd,Pt) complex anions bridged by Na-N in-teractions. 相似文献