Coordination compounds benzene complexes

The covalent character of mercury compounds and the corresponding abiUty to complex with various organic compounds explains the unusually wide solubihty characteristics. Mercury compounds are soluble in alcohols, ethyl ether, benzene, and other organic solvents. Moreover, small amounts of chemicals such as amines, ammonia (qv), and ammonium acetate can have a profound solubilizing effect (see COORDINATION COMPOUNDS). The solubihty of mercury and a wide variety of mercury salts and complexes in water and aqueous electrolyte solutions has been well outlined (5). 

Coordination compounds of dianionic dithiolene (S2C2 R2) and benzene-1,2-dithiolene (bdt = (S2C6H4) and their derivatives have been studied since the 1960s by Mossbauer spectroscopy [87] and other techniques. Nevertheless, many aspects of their electronic structure remained uncertain for a long time. The five-coordinate ferric complexes with two equatorial dithiolene ligands exhibit intermediate spin and show the Mossbauer parameters = 0.25-0.38 mm s and A q = 1.6-3.2 mm s For example, [Fe° mnt)2/ y] with two mnt ligands (=S2C2(CN)2) and an... 

Given the zwitterionic natnre of single carbenes, the possibility exists for coordinating solvents such as ethers or aromatic compounds to associate weakly with the empty p-orbital of the carbene. Several experimental stndies have revealed dramatic effects of dioxane or aromatic solvents on prodnct distribntions of carbene reactions. Computational evidence has also been reported for carbene-benzene complexes. Indeed, picosecond optical grating calorimetry stndies have indicated that singlet methylene and benzene form a weak complex with a dissociation energy of 8.7kcal/mol. ... 

Dimercury(I) n complexes are formed between aromatic compounds and Hg2(AsF6)2 in liquid S02 as solvent.113,121 Insoluble complexes with the ratio arene Hg2+ = 1 1 (arene = benzene, naphthalene, 2-methylnaphthalene, 2,6-dimethylnaphthalene, acenaphthene, fluor-anthrene, phenanthrene, anthracene, 9,10-dimethylanthracene or 1,3-dinitrobenzene) or 1 2 (arene = 9,10-benzophenanthrene) have been characterized by elemental analysis and, in some cases, by Raman spectrometry.113,120 The 13CNMR data allow the estimation of formation constants for the hexamethylbenzene, p-xylene and 1,4-dichlorobenzene complexes together with the chemical shifts for the bound substrates in these cases.121 Probably the coordination compounds of dimercury(I) salts with carbazole, dibenzofuran and diben-zothiophene are also n complexes.122... 

Other reports confirm similar reaction of C02 with metal alkoxide compounds. Benzene solutions of the alkoxide compounds Ti(OBu")4, Zr(OBu")4, Zr(OEt)4, Nb(OEt)5, and Fe(OEt)3 were found to absorb carbon dioxide in various amounts (151). Only Zr(OBu")4 reacted with an amount approaching one equivalent per metal complex. The solution ir spectra indicate formation of coordinated organic carbonates. From this evidence, equilibrium formation of the species M(0R) 1(02C0R) under 1 atm of C02 is inferred. 

As a first approximation, the reactions of pyridines with electrophiles can be compared with those of trimethylamine and benzene. Thus, pyridine reacts easily at the nitrogen atom with reagents such as proton acids, Lewis acids, metal ions, and reactive halides to form salts, coordination compounds, complexes, and quaternary salts, respectively. Under much more vigorous conditions it reacts at ring carbons to form C-substitution products in nitration, sulfonation, and halogenation reactions. 

Jonas and co-workers have pointed out that often a compromise must be found between sensitivity and resolution in NMR spectroscopy [76]. Line narrowing is optimum in regions of low supercritical fluid density (where the viscosity is low), but then the solubility of compounds is also low. Sometimes, admixtures with small amounts of low-viscosity solvents such as acetone may be tried to obtain a reasonable concentration of the compounds studied, i.e. coordination compounds such as (R-N=CH)2Mo(CO)4. However, line widths for this compound decrease by a factor of about four to six when comparing benzene-dg solutions to supercritical CO2 (with 8% acetone-de). The dispersion of the nitrogen chemical shift ensures identification of coordinated ligands by using NMR, in the above molybdenum complex, where A5( n) = -36 ppm) [75]. 

Iridium(III) compounds are generally more stable than those of iridium(lV), and iridium(III) coordination compounds include some of the most stable complexes known. On treatment with diethyl sulfide, iridium (IV) chloride loses chlorine, and the thio ether coordinates with the resulting iridium(III) chloride to form a mixture of stable, nonelectrolytic isomers of formula [Ir (C2H6)2S sCls]. The reaction is strongly dependent on the solvent it is accelerated in ethanol or acetone but inhibited completely in chloroform or benzene. Even in the presence of aqua regia, the same isomers are obtained—an indication of the extraordinary stability of iridium (III) complexes. 

The 6-coordinated compounds of tripositive cobalt are all octahedral, with the coordinated atoms at the six corners of an octahedron and the cobalt atom at the center. This arrangement has been demonstrated by X-ray diffraction and has also been proved by a study of isomerism in 6-coordinated. cobaltic compounds. An ion [C0X5Y] has no isomers. [C0X4Y2] has two isomers, ds and trans. If the complex were hexagonal and flat like a benzene ring, it would have to have three isomers. 

Lithium salts of 1-methylboratabenzene, l-dimethylamino-3,5-dimethylborata-benzene and l-bis(trimethylsilyl)amino-3,5-dimethylboratabenzene react with ScQs in toluene at elevated temperature to yield complexes 11, 12 and 13 having different structures and compositions (03OM5496). The structure 11 is characterized by two sandwich units doubly bridged by the chloride moieties. Compound 12 seems similar to 11 but one boratabenzene ligand is coordinated in an unusual (NBC) mode, while the second one is -coordinated. Compound 13 is mononuclear. 

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