Phenylcopper(I) clusters in the gas phase obtained by laser desorption/ionization from bis(dibenzoylmethane)copper(II)

Frański, Rafał; Kozik, T. A.; Staniszewski, Bartosz; Urbaniak, W.

doi:10.2478/s11532-010-0017-z

Cited by 4 publications

(3 citation statements)

References 18 publications

(24 reference statements)

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“…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. The presence of phenylcopper in the gas phase obtained by laser desorption/ ionization from bis(dibenzoylmethane)copper(II) has also been confirmed using tandem mass spectrometry (MS/MS) [41]. Phenylcopper and its clusters are used widely as reagents in organic synthesis [42].…”

Section: Introductionmentioning

confidence: 97%

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: 97%

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 growing interest on the coordination compounds of copper with various N-donor ligands, comes mainly from their capability of combining characteristic structural flexibility [13,14], mimicking of protein active sites [15][16][17], ease of preparation [18,19], and stabilization of both oxidation states of the metal usual in biological systems [20,21]. Considerable interest in various N and O donor ligands especially Schiff bases and their transition metal complexes have also grown in the areas of chemistry and biology due to biological activities, such as antiviral [22,23], antitumor [24,25], bactericidal [26,27], fungicidal [18] and nonlinear optical properties [28,29].…”

Section: Introductionmentioning

confidence: 99%

An azo-azomethine ligand and its copper(II) complex: Synthesis, X-ray crystal structure, spectral, thermal, electrochemical and photoluminescence properties

Eren

Köse

Kurtoğlu

et al. 2015

Inorganica Chimica Acta

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“…Because of copper reduction there are copper(I) containing ions. [21,22] Because of well-known high affinity of chloride anion toward silver cation, the spectrum of silver(I) acetate shows the presence of chloride containing ions (chlorides are present as impurities). The silver anion Ag − is worth noting.…”

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confidence: 99%

Formation of dimethylnickelate(I) and dimethylsilverate(I) anions in the gas phase from nickel(II) acetate and silver(I) acetate by laser desorption/ionisation

Frański

Gierczyk

2011

J. Mass Spectrom.

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Formation of dimethylnickelate(I) and dimethylsilverate(I) anions in the gas phase from nickel(II) acetate and silver(I) acetate by laser desorption/ionisation Species containing methylmetal moiety (H 3 C-metal bond) can be regarded as the simplest organometallic species. In nature, there are only two examples; the first well-known compound containing H 3 C-Co bond is methylcobalamin [1] and the second, definitely less known, is methylnickel. [2] Methylmercury cation (H 3 C-Hg + ) can be produced by some organisms, [3] but its presence in the environment in the past was related with several industrial processes. Obviously, there are a vast number of examples of compounds containing H 3 C-metal bond(s) prepared in the lab. It is also obvious that the higher the oxidation state of the metal, the more the methyl groups can be attached to it. Therefore, such metals like Pb(IV) or Pt(IV) are able to attach even four methyl groups, the respective compounds were already known in the first half of the 20th century. [4,5] The trimethylcopper(III), copper at rather rare oxidation state, is also worth mentioning. [6] Metals that are prone to form anions (metalates), e.g. Mn, Al, Cu, Pt, can attach more methyl groups than the actual oxidation state of the metal, and the respective 'pure' organometallic anions are formed. ] − , can be generated in the gas phase from nickel(II) acetate, silver(I) acetate and copper(II) acetate, by laser desorption/ionisation (LDI). Gas-phase studies belong to the fundamental studies. [14] It is reasonable to expect that the gas-phase ion chemistry will have great impact on the 21st century development of physical and organic chemistry. [15] Figure 1 shows the LDI mass spectra of nickel(II) acetate, silver(I) acetate and copper(II) acetate obtained in the negative ion mode. In each mass spectrum, there are ions consisting of metal and acetate groups (i), metal, acetate group(s) and methyl group (ii), metal and methyl groups (iii). It can be assumed that the ions containing methyl groups are formed from the ions containing acetate groups by the loss of CO 2 molecule(s).In the mass spectrum of nickel (II) − . The full-scan mass spectra (Fig. 1) concern the complicated processes that occurred in the expanding plume (e.g. ion-molecule reactions) which contained ions, neutrals and free electrons. Strictly, gas-phase decompositions are observed in the CID MS/MS experiments. Figure 2( CO] − , were also observed. The latter ion was not observed in full-scan mass spectrum but it is the most abundant in CID MS/MS spectrum at higher collision energy (CE, Fig. 2(b)). The [NiCH 3 (CH 3 COO)] − ion, which can be regarded as a direct precursor of [Ni(CH 3 ) 2 ] − ion, is also observed. However, the [Ni(CH 3 ) 2 ] − ion was not detected, even at higher CE (Fig. 2(b)). The CID MS/MS spectra of [Ni(CH 3 COO) 2 ] − and [NiCH 3 (CH 3 COO)] − ions (Fig. 2(c and d)) show that [Ni(CH 3 ) 2 ] − is formed from them.Full-scan mass spectra of silver(I) acetate and copper(II) acetate are less complicated than the above-d...

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Phenylcopper(I) clusters in the gas phase obtained by laser desorption/ionization from bis(dibenzoylmethane)copper(II)

Cited by 4 publications

References 18 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 azo-azomethine ligand and its copper(II) complex: Synthesis, X-ray crystal structure, spectral, thermal, electrochemical and photoluminescence properties

Formation of dimethylnickelate(I) and dimethylsilverate(I) anions in the gas phase from nickel(II) acetate and silver(I) acetate by laser desorption/ionisation

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