Diazonium Borofluorides. IV. The Preparation of Arylcopper Compounds

Bolth, F. A.; Whaley, Wilson M.; Starkey, Edgar B.

doi:10.1021/ja01248a004

Cited by 16 publications

(3 citation statements)

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“…Phenylcopper C 6 H 5 Cu) is the first organocopper compound and its synthesis was reported by Reich in 1923 as an impure product obtained in 60 % yield from phenylmagnesium bromide and cuprous iodide in ether [33]. Since then, several other methods for the synthesis of C 6 H 5 Cu have been reported [34][35][36][37][38][39]. Using 13 C NMR spectroscopy, Bertz et al [40] have shown that C 6 H 5 Cu is an equilibrium mixture of 'tetramer ' and 'trimer ' in dimethylsulfoxide (DMSO) solution.…”

Section: Introductionmentioning

confidence: 99%

Sequential metalation of benzene: electronic, bonding, magnetotropic and spectroscopic properties of coinage metalated benzenes studied by DFT

Tsipis

Gkarbounis

2015

J Mol Model

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A series of coinage metalated benzenes formulated as C6H6-nMn (M = Cu, Ag, Au, n = 1-5) were investigated by means of density functional theory (DFT) calculations. The structural, energetic, magnetotropic and spectroscopic properties of the coinage metalated benzenes were analyzed thoroughly and compared to the respective properties of the archetype aromatic benzene molecule. In contrast to the latter, the C6H6-nMn (M = Cu, Ag, Au, n = 1-5) molecules are predicted to be aromatic even in their excited triplet state. Excellent linear correlations between (I) the zz component of the nucleus independent chemical shift [NICSzz(1)] values and the total negative natural charge acquired by the carbocyclic ring, and (ii) the NICSzz(1) vs wavelength (λ) of the HOMO → LUMO transitions in the absorption spectra of the coinage metalated benzenes were established. The emission spectra of the coinage metalated benzenes were characterized by high [Formula: see text] values, particularly for the di-substituted - and p-isomers, with the highest [Formula: see text] value of 67 kcal mol(-1) calculated for the m-M6H4Au2 species. The bonding pattern of the coinage metalated benzenes was analyzed thoroughly by means of a multitude of electronic structure calculation methods [natural bond orbital (NBO), atoms-in-molecules (AIM), electron localization function (ELF), reduced density gradient (RDG) and Sign(λ 2(r))ρ(r) functions]. Our findings indicate whole classes of new coinage metalated benzenes (mono-, di-, tri-, four- and five-substituted) opening a new chemistry for the coinage metalated benzenes, indicating that their chemistry will be worthwhile studying both experimentally and theoretically in the future. Graphical Abstract The complete series of coinage metalated benzenes were investigated by density functional theory methods. The structural, energetic, bonding, magnetotropic and spectroscopic properties of the coinage metalated benzenes were analyzed thoroughly. In contrast to the archetype aromatic benzene molecule, the coinage metalated benzenes are predicted to be aromatic even in their excited triplet state.

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Section: Introductionmentioning

confidence: 99%

Sequential metalation of benzene: electronic, bonding, magnetotropic and spectroscopic properties of coinage metalated benzenes studied by DFT

Tsipis

Gkarbounis

2015

J Mol Model

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“…The state of ligation of (Cu I An) is uncertain; (Cu I Ph) has been reported to be highly sensitive to moisture but to be stabilised against protonolysis on ligation by pyridine. 46 Ligation of (Cu I An) by MeCN could afford comparable stabilisation and hence facilitate its reaction with 1.…”

Section: Methodsmentioning

confidence: 99%

“…For the production of 4-methoxyphenol, 6, we have excluded both the thermolysis of 1 and the hydrolysis of (Cu III An) 2+ formed by simple addition of An • to Cu 2+ [Results (ix)]. 47 Nevertheless, an alternative involvement of Cu(III) is needed as the precursor to 6 since both organocopper(I) 46 and organocopper(II) 11 species undergo protonolysis not hydrolysis on reaction with water. First,…”

Section: Methodsmentioning

confidence: 99%

An investigation of the reduction in aqueous acetonitrile of 4-methoxybenzenediazonium ion by the tetrakis(acetonitrile)Cu(i) cation catalysed by hydrogenphosphate dianion

et al. 2007

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In aqueous acetonitrile containing a phosphate buffer, 4-methoxybenzenediazonium ion is reduced by one or more of the partially aquated cations derived from tetrakis(acetonitrile)Cu(I) cation in this medium. Investigation of the reaction mechanism indicates the rate determining step to be the association of the diazonium ion with the hydrogenphosphate dianion to give an adduct which then undergoes reduction by Cu(I). The reaction gives a range of products which have been identified and quantified by GC. One of these, 4-methoxyphenol was unexpected in the reducing conditions; its presence could be explained by the disproportionation of a 4-methoxyphenylcopper(II) complex giving bis(4-methoxyphenyl)copper(III) which reacts with water to produce the phenol and an equivalent amount of methoxybenzene. A scheme is proposed which accounts for all the observed products and computer modelling gives a satisfactory description of the distributions of the five major products as functions of the relative proportions of the reactants for dilute conditions and those where the reductant is in excess. When the diazonium ion is in excess, the behaviour of the model and the experimental reactant accountability suggest the occurrence of additional reactions which give products unobserved by GC.

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Preparation of Aromatic Fluorine Compounds from Diazonium Fluoborates

Roe¹

2011

Organic Reactions

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An excellent method for the introduction of fluorine into the aromatic nucleus, described by Balz and Schiemann, has been extensively extended. The method involves two steps, first, the preparation and solution of a dry diazonium fluoborate, and second, the controlled decomposition of this salt by heat to yield an aromatic fluoride, nitrogen, and boron trifluoride. This phenomenon which makes possible, the Schiemann reaction is the remarkable stability of the dry diazonium borofluoride. The overall yields are satisfactory and no special apparatus is necessary. The reaction may be carried out on a wide variety of amines. The effect of the Schiemann reaction on other groups present in the ring is discussed in detail.

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Diazonium Borofluorides. IV. The Preparation of Arylcopper Compounds

Cited by 16 publications

References 0 publications

Sequential metalation of benzene: electronic, bonding, magnetotropic and spectroscopic properties of coinage metalated benzenes studied by DFT

Sequential metalation of benzene: electronic, bonding, magnetotropic and spectroscopic properties of coinage metalated benzenes studied by DFT

An investigation of the reduction in aqueous acetonitrile of 4-methoxybenzenediazonium ion by the tetrakis(acetonitrile)Cu(i) cation catalysed by hydrogenphosphate dianion

Preparation of Aromatic Fluorine Compounds from Diazonium Fluoborates

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