Experimental and theoretical studies of the binding interaction between copper(I) cation and the carbonyl group

Than, Soe; Maeda, Hideaki; Irie, Maki; Kikukawa, Kiyoshi; Mishima, Masaaki

doi:10.1016/j.ijms.2007.02.037

Cited by 22 publications

(21 citation statements)

References 38 publications

(61 reference statements)

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“…That is, a simple additive rule does not hold for the dimeric complex. A similar attenuation factor of 1.6 was obtained for Li + and Cu + complexation energies 10, 11. In addition, the good linearity of the correlation reveals that the effects of all the substituents are consistently reduced in the dimeric adduct ion system compared to those in the monomeric complex.…”

Section: Resultssupporting

confidence: 70%

“…Since the ΔLaCB[L 2 ] values indicate the effect of two acetophenone molecules on the stability of the La(OMe)

_{2}^{+}

complexes, the slope of a linear relationship between ΔLaCB for the monomeric complex (La(OMe)

_{2}^{+}

L) and ΔGB may be assumed to be 0.51 (=1.02/2) in the first approximation, indicating that the substituent effect is significantly reduced in the La(OMe)

_{2}^{+}

complex compared to that in the protonated system. With respect to the magnitude of the substituent effect for the monomeric complex we recently found that the substituent effect for the free energy change of the second addition of a ligand to a monomeric complex ion is smaller than that for the first addition of a ligand to a metal ion based on the theoretical calculation 10–12. Hence, the DFT calculations were conducted for neutral molecules, monomeric, and dimeric complexes.…”

Section: Resultsmentioning

confidence: 99%

“…The contribution of the resonance effect involved in the stability of the La(OMe)

_{2}^{+}

complex will be described in terms of the Yukawa–Tsuno (Y–T) equation (Eqn 13)14–17 as applied successfully in the previous studies 10, 11, 18, 19 …”

Section: Resultsmentioning

confidence: 99%

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Gas‐phase basicities of acetophenones toward lanthanum cation [La(OMe)]

Than

Badal

Itoh

et al. 2010

J of Physical Organic Chem

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The relative free energy changes (lanthanum cation basicity, LaCB[L2]) for the reaction [La(OMe)2]L 2+ ⇌ La(OMe) 2+ + 2L were determined in the gas phase for m‐ and p‐substituted acetophenones based on the measurement of ligand exchange equilibria using an FT‐ICR mass spectrometer. The substituent effect on ΔLaCB[L2] of acetophenone is described in terms of the Yukawa–Tsuno equation, ΔG = ρ(σ° + r+ Δ σ R+), with a ρ value of −11.2 and an r+ value of 0.49. From this result, a ρ value of −7.0 and an r+ value of 0.49 were estimated for the monomeric complex [LLa(OMe) 2+] with the aid of theoretical calculations. This ρ value was found to be significantly smaller than that for protonation, and even smaller than Li+ basicity. Such a small ρ value has been attributed to the largely ionic (ion–dipole interaction) nature of the bonding interaction between La(OMe) 2+ and the carbonyl oxygen atom and, in part, to the long distance between La(OMe) 2+ and the substituent. Contrary to the ρ value, the r+ value is identical in both La(OMe) 2+ and Li+ basicities, suggesting that the r+ value of 0.49 can be regarded as a limiting one in a series of Lewis cation basicities of the acetophenone system, H+ (0.86) > Me3Si+ (0.75) > Me3Ge+ (0.71) > Cu+ (0.60) > Li+ = La(OMe) 2+ (0.49). Since the binding interaction between La(OMe) 2+ or Li+ and a neutral ligand is mostly electrostatic, the moderate r+ was interpreted to result from the redistribution of the induced positive charge within the acetophenone moiety upon binding with a metal ion rather than transfer of positive charge from a metal ion to the aromatic moiety. Copyright © 2010 John Wiley & Sons, Ltd.

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Section: Resultssupporting

confidence: 70%

“…Since the ΔLaCB[L 2 ] values indicate the effect of two acetophenone molecules on the stability of the La(OMe)

_{2}^{+}

complexes, the slope of a linear relationship between ΔLaCB for the monomeric complex (La(OMe)

_{2}^{+}

L) and ΔGB may be assumed to be 0.51 (=1.02/2) in the first approximation, indicating that the substituent effect is significantly reduced in the La(OMe)

_{2}^{+}

Section: Resultsmentioning

confidence: 99%

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Gas‐phase basicities of acetophenones toward lanthanum cation [La(OMe)]

Than

Badal

Itoh

et al. 2010

J of Physical Organic Chem

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“…This is true of Li + , Na + , Mg 2+ [77], Al + [78], Mg + , Ca + and Zn + [79]. In the case of acetophenones with Cu + (one and two ligands), the complex is also bent, with an angle close to 135 • , the metal being on the side of the methyl group [82]. In contrast, the B3LYP geometry of Me 2 CO Cu + is linear [16].…”

Section: Structure Of Cation/molecule Adductsmentioning

confidence: 97%

“…The upper part of the scale was explored in 1998 by the HPMS method [146]. Two specific series, ring-substituted acetophenones [82] and pyridines [147], were studied in 2007 by the FTICR method. [82,[145][146][147] are collected in Table 6.…”

Section: Coppermentioning

confidence: 99%

Gas‐Phase Cation Affinity and Basicity Scales

Laurence

Gal

2009

Lewis Basicity and Affinity Scales

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The study of the formation of complexes between cations and chemical species in the gas phase offers the unique possibility of measuring the intrinsic (i.e. free of solvent and counter ion influences) Lewis basicity of these species. Although the charge-transfer component of the interaction energy in cation adducts is normally smaller than the electrostatic and polarization components, gas-phase cations are generally considered as archetypal Lewis acids because the full positive charge of the naked cation allows strong binding with classical Lewis bases. In fact, almost any entity bearing some electron density, such as the rare gases, can form complexes with cations that may be observable in the gas phase.There is a large array of cations that have been studied in the gas phase for their interaction with Lewis bases (generally neutral organic molecules) and are still being actively investigated today. The most studied is the proton [1-6]. This special cation will not be dealt with in this chapter (however, see Section 1.3 in Chapter 1), since the proton and its transfer serve to define the Brönsted acids and bases, as opposed to Lewis acids and bases, which do not exchange protons. Moreover, although the proton and a cation with an empty orbital may be seen as identical from the point of view of the Lewis theory, the special 'electronic structure' of the proton (in fact the absence of any electron) makes the proton affinity and basicity scales completely different, qualitatively and quantitatively, from any other cation scales. A significant part of the studies of the interaction of gas-phase metal cations with organic molecules was devoted to their chemical reactivity: bond insertion, bond cleavage, elimination and so on. This aspect is not considered here, although some of these reactions may be used as indirect routes for the formation of cation/molecule adducts.Apart from the proton, experimental studies have focused primarily on the binding of alkali metal cations and transition metal monocations. Few studies have considered alkaline Lewis Basicity and Affinity Scales: Data and Measurement

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Kinetic Study on Reactions of O‐Y‐substituted Phenyl Thionobenzoates with Quinuclidine: Factors Governing Reactivity and Reaction Mechanism

Yang

Kim

2015

Bulletin Korean Chem Soc

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Second‐order rate constants (k quin) for the reactions of O‐Y‐substituted phenyl thionobenzoates (3a–3i) with quinuclidine have been measured spectrophotometrically. Comparison of k quin with the rate constants reported previously for the corresponding reactions with benzylamine (k BzNH2) has revealed that quinuclidine is less reactive than benzylamine toward 3a–3i although the former is 2.1 pK a units more basic than the latter. Steric hindrance exerted by quinuclidine has been suggested to be responsible for the decreased reactivity of the tertiary amine. The Brønsted‐type plot for the reactions of 3a–3i with quinuclidine is linear with βlg = −0.37. The Hammett plot correlated with σ Y o constants exhibits many scattered points ( R 2 = 0.982). In contrast, the Yukawa‐Tsuno plot results in an excellent linear correlation ( R 2 = 0.9992) with ρ Y = 0.96 and r = 0.51, indicating that a negative charge develops partially on the O atom of the leaving group. Thus, the reactions of 3a–3i with quinuclidine have been concluded to proceed through a concerted mechanism in which expulsion of the leaving group is advanced only a little in the rate‐determining transition state.

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Experimental and theoretical studies of the binding interaction between copper(I) cation and the carbonyl group

Cited by 22 publications

References 38 publications

Gas‐phase basicities of acetophenones toward lanthanum cation [La(OMe)]

Gas‐phase basicities of acetophenones toward lanthanum cation [La(OMe)]

Gas‐Phase Cation Affinity and Basicity Scales

Kinetic Study on Reactions of O‐Y‐substituted Phenyl Thionobenzoates with Quinuclidine: Factors Governing Reactivity and Reaction Mechanism

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