Search results for "Ordination"
showing 10 items of 1367 documents
Molecular “Floppyness” and the Lewis Acidity of Silanes: A Density Functional Theory Study
2001
A comprehensive set of Lewis acid-base adducts of silanes was investigated by means of the density functional theory geometry optimization [B3LYP/6−31G(d)], and thermochemical calculations, [B3LYP/6−311+G(2d,p)//B3LYP/6−31G(d)]. Complex formation was found to weaken Si−Cl and Si−Br bonds more than Si−F or Si−H bonds. Comparable distances between Si and a Lewis base L (L = NH3, OH2, F−) are shorter in hexa- than in pentacoordinated complexes. The molecular structures of the pentacoordinated Si complexes allowed for a mapping of an SN2 reaction pathway by correlating the lengths of the Si−X and Si−L bonds. Complex formation was found to be exothermic for most of the coordination compounds, an…
Synthesis of a rod-based porous coordination polymer from a nucleotide as a sequential chiral inductor
2021
We report the two-step synthesis of a novel chiral rod-based porous coordination polymer (PCP). The chemical approach consists of the use of a previously prepared bis(ethylenediamine) copper monomer [Cu(en)]2(NO3)2 [where en = ethylenediamine] reacting with the cytidine 5′-monophosphate (CMP) nucleotide. The bis(ethylenediamine) copper compound—stabilized by axial coordination of nitrate counter-anions—reacts in the presence of sodium salt of CMP to yield right-handed copper(II) chains of P helicity with formula [Cu2(en)2(CMP)2]·5H2O (1). The axial coordination of the CMP2- ligands through the N3 and O2 sites (free nitrogen and carbonyl groups) of the cytosine nucleobase and oxygen atoms of…
Solvent-Free Synthesis of a Pillared Three-Dimensional Coordination Polymer with Magnetic Ordering
2015
A new magnetic coordination polymer, [Fe(bipy)(im)2] (bipy = 4,4-bipyridine and im = imidazole), has been synthesized in a solvent-free reaction. Structural analysis reveals a pillared 3D coordination polymer composed by neutral layers, formed by iron(II) and imidazolate linkers, interconnected by bipy ligands which serve as pillars. Magnetic measurements show that the material magnetically orders at low temperatures (Tc = 14.5 K) as a weak ferromagnet, likely due to a spin canting.
Cu2+ Coordination Properties of a 2-Pyridine Heptaamine Tripod: Characterization and Binding Mechanism
2009
The synthesis, protonation, and Cu(2+) coordination chemistry of a tripodal heptaamine ligand (L(1)) functionalized with 2-pyridine fragments at the ends of its three branches are reported. L(1) presents six relatively high protonation constants followed by much more reduced constant that as indicated by the UV-vis and NMR data, occur on the pyridine fragments. p[H]-metric, ESI/MS(+), EPR and UV-vis data show that L(1) is able to form mono-, di-, and trinuclear Cu(2+) complexes. Slippage movements and molecular reorganizations have been observed to occur as a function of p[H] in the 1:1 Cu(2+) complexes. The kinetic studies showed that the complex formation is fast and proceeds through a di…
Dinuclear copper(II) complexes as testing ground for molecular magnetism theory
2019
Abstract A leitmotiv in the field of molecular magnetism is the study of the electron exchange (EE) magnetic interactions among distant metal centers through the corresponding bridging ligands in polynuclear coordination compounds. The present review provides a historical perspective on the use of dinuclear copper(II) complexes with either simple inorganic or extended organic bridging ligands as experimental and theoretical models for the fundamental research on the relative importance of the spin delocalization and spin polarization mechanisms of the EE interaction across σ- and π-type orbital pathways. Particular focus is placed on the work by Professor Miguel Julve, outstanding researche…
Direct monitoring of spin state in dinuclear iron(II) coordination compounds
2001
So far there has been no direct method to determine the spin state of molecules in dinuclear iron(II) compounds. The molecular fractions of high-spin (HS) and low-spin (LS) species have been deduced from magnetic susceptibility and zero-field Mossbauer spectroscopy data irrespective of whether they belong to LS–LS, LS–HS and HS–HS pairs. However, the distinction of pairs becomes possible if Mossbauer measurements are carried out in an external magnetic field. The proposed method opens new possibilities in the study of spin crossover phenomena in dinuclear compounds.
Thermal, Pressure and Light Induced Spin Transition in the Two-Dimensional Coordination Polymer [Fe(pmd)2[Cu(CN)2]2]
2008
[EN] A complete structural, calorimetric, and magnetic characterisation of the 2D coordination spin crossover polymer {Fe(pmd)(2)[Cu(CN)(2)](2)} is reported. The crystal structure has been investigated below room temperature at 180 K and 90 K, and at 30 K after irradiating the sample at low temperature with green light ( lambda = 532 nm). The volume cell contraction through the thermal spin transition is only 18 angstrom(3) which is lower than the usually observed value of around 25-30 angstrom(3) while the average Fe-N bond distances decrease by the typical value of about 0.19 angstrom. The structural data of the irradiated state indicate that the high spin state is well induced since the …
Spin-State-Dependent Redox-Catalytic Activity of a Switchable Iron(II) Complex
2017
The spin state of catalytically active 3d metal centers plays a significant role for their activity in enzymatic processes and organometallic catalysis. Here we report on the catalytic activity of a Fe(II) coordination compound that can undergo a cooperative switch between low-spin (LS) and high-spin (HS) states. Catalytic measurements within 291 - 318 K temperature region reveal a drastic drop of the catalytic activity upon conversion of metallic centers from the LS to the HS form. For a thermoswitchable [Fe(NH2trz)3]Br2 complex (Tup = 305 K), an activation energy is found to be considerably lower for the LS state (158 kJ mol-1) comparing to the HS state (305 kJ mol-1). Mossbauer analysis …
Experimental Investigations and ab Initio Studies on Hexacoordinated Complexes of Dichlorosilane
1998
Dichlorosilane, SiH2Cl2, forms two different kinds of coordination compounds with pyridine and 3-picoline: the simple adduct trans-SiH2Cl2(L)2 and the ionic complex [SiH2(L)4]Cl2·4CHCl3 (L = pyridine, 3-picoline). The adducts trans-SiH2Cl2(py)2, 1, and trans-SiH2Cl2(3pic)2, 2, form directly from the reaction of bis(dichlorosilyl)methylamine, NMe(SiHCl2)2 with pyridine (py), and 3-picoline (3pic). Reaction of 1 with an excess of pyridine in chloroform yielded [SiH2(py)4]Cl2·4CHCl3, 3. The molecular and crystal structures of 1−3 were investigated by single-crystal X-ray diffraction. The Si atoms of all three compounds are hexacoordinated and lie on centers of inversion. The basic structural …
Reactivity of CuI and CuBr toward Dialkyl Sulfides RSR: From Discrete Molecular Cu I S and Cu I S Clusters to Luminescent Copper(I) Coordination Pol…
2015
The 1D coordination polymer (CP) [(Me2S)3{Cu2(μ-I)2}]n (1) is formed when CuI reacts with SMe2 in n-heptane, whereas in acetonitrile (MeCN), the reaction forms exclusively the 2D CP [(Me2S)3{Cu4(μ-I)4}]n (2) containing “flower-basket” Cu4I4 units. The reaction product of CuI with MeSEt is also solvent-dependent, where the 1D polymer [(MeSEt)2{Cu4(μ3-I)2(μ2-I)2}(MeCN)2]n (3) containing “stepped-cubane” Cu4I4 units is isolated in MeCN. In contrast, the reaction in n-heptane affords the 1D CP [(MeSEt)3{Cu4(μ3-I)4}]n (4) containing “closed-cubane” Cu4I4 clusters. The reaction of MeSPr with CuI provides the structurally related 1D CP [(MeSPr)3{Cu4(μ3-I)4}]n (5), for which the X-ray structure has…