Temperature dependence of the vibration-vibration transfer rates from CO2 and N2O excited in the (0001) vibrational level to 14N2 and 15N2 molecules

V-V transfer rates from CO₂ and N₂O excited in the (00⁰1) vibrational level to ¹⁴N₂ and ¹⁵N₂ are determined from 150 to 1200 K using the laser fluorescence method, and compared with values calculated on the basis of dipole-quadrupole interactions.     

New Bimetallic Ni–Rh Carbonyl Clusters: Synthesis and X-ray Structure of the [Ni7Rh3(CO)18]3?, [Ni3Rh3(CO)13]3? and [NiRh8(CO)19]2? Cluster Anions

The reaction of the [Ni₆(CO)₁₂]²⁻ dianion with [Rh(COD)Cl]₂ (COD = cyclooctadiene) in acetone affords a mixture of bimetallic Ni–Rh clusters, mainly consisting of the new [Ni₇Rh₃(CO)₁₈]³⁻ and [Ni₈Rh(CO)₁₈]³⁻ trianions. A study of the reactivity of [Ni₇Rh₃(CO)₁₈]³⁻ led to isolation of the new [Ni₃Rh₃(CO)₁₃]³⁻ and [NiRh₈(CO)₁₉]²⁻ anions. All these new bimetallic Ni–Rh carbonyl clusters have been isolated in the solid state as tetrasubstituted ammonium salts and have been characterised by elemental analysis, X-ray diffraction studies, ESI-MS and electrochemistry. The unit cell of the [NEt₄]₃[Ni₇Rh₃(CO)₁₈] salt contains two orientationally-disordered ν₂-tetrahedral [Ni₇Rh₃(CO)₁₈]³⁻ trianions with occupancy factors of 0.75 and 0.25. Besides, their inner Ni₃Rh₃ octahedral moieties show two cis sites purely occupied by Rh atoms, two trans sites purely occupied by Ni atoms and the remaining two cis sites are disordered Ni and Rh sites with respective occupancy fraction of 0.5. At difference from the parent [Ni₇Rh₃(CO)₁₈]³⁻, the octahedral [Ni₃Rh₃(CO)₁₃]³⁻ displays an ordered distribution of Ni and Rh atoms in two staggered triangles. The [NiRh₈(CO)₁₉]²⁻ dianion adopts an isomeric metal frame with respect to that of the [PtRh₈(CO)₁₉]²⁻ congener. As a fallout of this work, new high-yield synthesis of the known [Ni₆Rh₃(CO)₁₇]³⁻ and [Ni₆Rh₅(CO)₂₁]³⁻, as well as other currently-investigated bimetallic Ni–Rh clusters have been obtained.     

铜氨络离子的形成和空间构型的探究

基于化学平衡的原理,通过简单的计算解释了氢氧化铜溶于氨水的反应机理,同时基于价键理论和Jahn-Teller效应来阐述铜氨络离子以及其他铜离子配合物的形成过程.     

Investigation of Protonation of the Tetraazamacrocyclic Complex of Gold(III) [Au(C14H22N4)]+ in Water. Synthesis and Crystal and Molecular Structures of [Au(C14H23N4)](ClO4)2

The equilibrium of protonation of tetraazamacrocyclic complex of gold(III) [AuL]⁺ (L = 5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,6,11,13-tetraenato(2-)) in a water solution has been investigated. A monoprotonated tetraazamacrocyclic metallocomplex with two inequivalent (iminate and imine) six-membered chelate cycles and charge 1- was obtained and isolated for the first time. The compound [AuHL](ClO₄)₂ was characterized by chemical analysis, IR and UV-VIS spectroscopy, powder and single crystal X-ray diffraction. The proton was shown to be attached to the β-carbon of one of the two six-membered chelate rings of the macrocycle. Crystal data for [AuHL](ClO₄)₂ are: a = 7.693(1) Å, b = 17.366(2) Å, c =15.172(2) Å; β = 96.82(1)°, V = 2012.6(4) ų, Z = 4, d _calc = 2.123 g/cm³, space group P2₁/c. The structure is built from practically planar [Au(C₁₄H₂₃N₄)]²⁺ cations and perchlorate anions [ClO₄]⁻.Original Russian Text Copyright © 2004 by V. A. Afanasieva, I. V. Mironov, L. A. Glinskaya, R. F. Klevtsova, and L. A. Sheludyakova__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1059–1066, November–December, 2004.     

Cation Dependent Formation of Hybrid Organic–Inorganic Frameworks Based on the Strandberg-Type Polyanion [(O2CCH2PO3)2Mo5O15]6? and Cu2+ Ions

We present the first examples of materials based on the Strandberg type polyanion [(O₂CCH₂PO₃)₂Mo₅O₁₅]⁶⁻, linked by Cu²⁺ centers via coordination to the carboxylate functions of the polyanion. Simple one-pot reaction of Rb₄KNa[(O₂CCH₂PO₃)₂Mo₅O₁₅]·H₂O with CuCl₂·2H₂O in aqueous acidic media followed by crystallization resulted in the three hybrid organic–inorganic materials {K_2.6Rb_1.4[(PO₃CH₂CO₂)₂Mo₅O₁₅Cu(H₂O)₃]·7H₂O} _n (KRb-1), {Na₂Cs₃[(PO₃CH₂CO₂)₂Mo₅O₁₅(Cu(H₂O)₂Cl)]·6H₂O} _n (NaCs-2) and {Na_2.75Rb_1.25[(PO₃CH₂CO₂)₂Mo₅O₁₅Cu(H₂O)₃]·9H₂O} _n (NaRb-3), which were characterized by single-crystal X-ray diffraction, IR, TGA and elemental analysis. All three compounds are 1:1 polymers of the polyanion and the Cu²⁺ centers are all five-coordinate with two carboxylate oxygens in a trans fashion. However, the chains in KRb-1, NaCs-2 and NaRb-3 are packed differently along b leading to different solid state structures, indicating an important role of the alkali counter cations. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. Dedicated to Professor Dieter Fenske on the occasion of his 65th birthday     

Study on the interactions between anti-tumor metal complexes and mononucleotides using trans -[en2Os(η2-H2)(CF3SO3)](CF3SO3) as a 1H NMR probe in a competitive mode

The interaction of several anti-tumor metal complexes with dGMP have been investigated using trans-[en₂Os(η²-H₂)]²⁺ as a ¹H NMR probe in a competitive mode. Me₂SnCl₂, Bu₂SnCl₂, Et₂Sn(phen)Cl₂ and Et₂SnCl₂can bind to dGMP mainly via phosphate; Cp₂TiCl₂ binds to dGMP mainly via phosphate and N₇. The binding constant for (CH₃)₂SnCl₂ binding to phosphate of dGMP exceeds 2.71×10⁴. The binding constant for Cp₂TiCl₂ to phosphate is even greater than that of Sn(IV). Cis-platin has high affinity for both N₇ and phosphate, but mainly for N₇. Binding of the probe to N₇ of dGMP reduces the binding affinity for phosphate of the same dGMP molecule by a factor of 5 to 6. Much the same factor is expected to apply to other metals containing agents interacting with dGMP.     

Study on the covalence of Cu and chemical bonding in an inorganic fullerene-like molecule, [CuCl]20[Cp*FeP5]12 [Cu-(CH3CN)+2Cl-]5, by a density functional approach

The electronic structure and chemical bonding in a recently synthesized inorganic fullerene-like molecule, [CuCl]₂₀[Cp*FeP₅]₁₂[Cu-(CH₃CN) ⁺ ₂Cl⁻]₅ has been studied by a density functional approach. Geometrical optimization of the three basic structural units of the molecule is performed with Amsterdam Density Functional Program. The results are in agreement with the experiment. Localized MO’s obtained by Boys-Foster method give a clear picture of the chemical bonding in this molecule. The reason why CuCl can react with Cp*FeP₅ in solvent CH₃CN to form the fullerene-like molecule is explained in terms of the soft-hard Lewis acid base theory and a new concept of covalence.