Pyridine coordination compounds

Ch. 2 CT-Pyridine Coordination Compounds with Nontransition Metals Ch. 3 CT-Pyridine Coordinarion Compounds with Transition Metals... 

Ch. 3 (Continued) CT-Pyridine Coordination Compounds with Transition Metals Vol. 14, Pt. 6C... 

Measurements on copper) I) chloride show the vapour to be the dimer of formula CU2CI2, but molecular weight determinations in certain solvents such as pyridine show it to be present in solution as single molecules, probably because coordination compounds such as py -> CuCl (py = pyridine) are formed. 

The mechanisms of the electrophilic substitutions in the isoxazole nucleus have not yet been studied. They should not differ fundamentally from those usually accepted for the substitution of aromatic systems but the structural specificity of the isoxazole ring might give rise to some peculiarities, as recently specially discussed.One important point is that isoxazole shows a clearcut tendency to form coordination compounds. Just as pyridine and other azoles, isoxazoles coordinate with halogens and the salts of heavy metals, for example of cadmium,mercury,zinc. Such coordination... 

Comparative studies [1127] of the kinetics of decomposition of similar salts containing related pyridine ligands have been used to investigate the strength of M—N bonds in coordination compounds. Non-isothermal DSC measurements were used to determine values of E for the reactions... 

Coordination compounds containing bidentate ligands are often thermally more stable than those comprised of related monodentate ligands, e.g. ethylenediamine (en) complexes dissociate at a higher temperature than those of ammonia or pyridine. Compounds containing a ring structure, such as coordinated salicylaldehyde (sal) and acetyl-acetonate (acac), are particularly stable, and may often be sublimed... 

The divalent Co(salen) complex (69a) is one of the most versatile and well-studied Co coordination compounds. It has a long and well-documented history and we shall not restate this here. Recent applications of (69a) as both a synthetic oxygen carrier and as a catalyst for organic transformations are described in Sections 6.1.3.1.2 and 6.1.4.1 respectively. Isotropic shifts in the HNMR spectrum of low-spin Co(salphn) (69b) were investigated in deuterated chloroform, DMF, DMSO, and pyridine.319 Solvent-dependent isotropic shifts indicate that the single unpaired electron, delocalized over the tetradentate 7r-electron system in CHCI3, is an intrinsic property of the planar four-coordinate complex. The high-spin/low-spin equilibrium of the... 

The chemistry of coordination compounds comprises an area of chemistry that spans the entire spectrum from theoretical work on bonding to the synthesis of organometallic compounds. The essential feature of coordination compounds is that they involve coordinate bonds between Lewis acids and bases. Metal atoms or ions function as the Lewis acids, and the range of Lewis bases (electron pair donors) can include almost any species that has one or more unshared pairs of electrons. Electron pair donors include neutral molecules such as H20, NH3, CO, phosphines, pyridine, N2, 02, H2, and ethyl-enediamine, (H2NCH2CH2NH2). Most anions, such as OH-, Cl-, C2042-, and 11, contain unshared pairs of electrons that can be donated to Lewis acids to form coordinate bonds. The scope of coordination chemistry is indeed very broad and interdisciplinary. 

In the case of dense, surface-grafted polymer brush thin hlms, cross-links are introduced by the simple addition of solutions containing bis(Pd -pincer) compounds 4a or 4b to grafted PVP brushes (Loveless et al. 2006). Because the association constants for pyridine coordination are similar, the uptake of 4a and 4b from equimolar solutions into the PVP brushes (at constant grafting density and molecular weight) is effectively equivalent, producing samples with comparable structure (number and placement of cross-links). 

In these discussions, we have focused attention on details of the physical measurements which confer understanding of structure in pyridine based compounds bond lengths, bond angles, electronic levels in both ground and excited states, and the involvement of solvation, complexation and other environmental features. In the latter, we have, out of necessity, restricted ourselves generally to complexes in which the role of the pyridine structure is of paramount interest, for the whole of the available space could have been filled with lists of complexes incorporating these structures, but where they were of subordinate interest to some other feature, typically the mode of coordination of metallic ions. 

The present paper describes the synthesis of N-(2-hydroxyethyl)-3,5-dimethylpyrazole and the synthesis of the tosylated compound N-(2-p-tol-uenesulfonylethyl)-3,5-dimethylpyrazole which can be used for the synthesis of larger chelating ligands. The tosylation is carried out in a water/acetone mixture, unlike most classical tosylations, which are performed in pyridine.7 A high yield of pure tosylated product is obtained from this reaction. A water/acetone mixture as the solvent for the synthesis of other tosylates may very well be also successful. Since the compound N-(2-hydroxyethyl)-3,5-dimethylpyrazole may itself act as a didentate N,0 ligand in coordination compounds with transition metal ions,9 an example using Cu(II) is provided below. 

Pyridine readily forms stable coordination compounds. Thus, boron, aluminum and gallium trihalides react at 0°C in an inert solvent to give 1 1 adducts (cf. 85). Steric factors are important, and a-substituents decrease the ease of reaction. This is illustrated by the heats of reaction of pyridine, 2-methylpyridine and 2,6-dimethylpyridine with boron trifluoride which are 101.3, 94.1 and 73.2 kJ mol-1, respectively. The marked decrease in exothermicity here should be contrasted with the small steric requirement of the proton as shown by the pA., values of substituted pyridines (see Section 3.2.1.3.4). 

Other addition compounds of Hg2(N03)2 with aromatic amines97 contain two molecules of the N ligand and one molecule of Hg2(N03)2 with 4-fluoroaniline four molecules of the ligand are coordinated.97 Similar results have been obtained with Hg2(N03)2 or Hg2(C104)2 and mono-, di- and tri-substituted anilines, pyridines and l,4-diazabicyclo[2.2.2]octane.101,102 Coordination compounds are also formed with aminopyridine, trichloroacetaminopyridine and aminochloropyridine.103 The X-ray structure determination of the coordination compound between Hg2(C104)2 and 3-aminopyridinium perchlorate revealed the structure (12).103... 

CN depends not only on the composition of a coordination compound, but also on the type of a- and n-bonds present in it. Chromium carbonyl-pyridine complexes are the classic example to illustrate the difficult task of determining unambiguously the coordination numbers. Only a-bonds are present in Cr(py)(CO)5 and CN = 6 (12). However, in the a, n-complex 13, as well as in 9, the coordination number is quite questionable (compare formulae 9 IT). 

Many examples of electrochemically prepared anionic complexes are known [202,506,507,551]. Among them, the coordination compounds with ammonium cations are of interest [506,507]. In these syntheses, it is possible to vary the composition of complexes of the type [(R4N)mMX ]. Thus, similar complexes (R = Me, X = SCN, m = 2, 3, 4 m = 4, 6) were obtained by dissolution of metals (Mn, Fe, Co, Cu, Zn, Cd) in aqueous medium, containing (Me4N)SCN [561], Analogous syntheses with use of pyridine, 2,2 -bipy, and 1,10-phen (L) lead to neutral complexes, for instance (3.241) [561] ... 

As a result of interaction of 843 and pyridine, the adduct 845 is formed [53], The structures of coordination compounds 844 and 845 were proved by x-ray diffraction. As shown above (Sec. 3.4.3.2), the direct ammonia synthesis [55,56] with participation of various ligands (especially aliphatic, aromatic, and heterocyclic amines, aminoalcohols), elemental metals (or their oxides), and NH4SCN in mostly non-aqueous media, opens definite possibilities for obtaining thiocyanate complexes. In this respect, transformation (4.9) should be mentioned [57] ... 

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