Inhibition of Alkali Metal Reduction of 1-Adamantanol by London Dispersion Effects

A series of alkali metal 1-adamantoxide (OAd1) complexes of formula [M(OAd1)(HOAd1)2], where M=Li, Na or K, were synthesised by reduction of 1-adamantanol with excess of the alkali metal. The syntheses indicated that only one out of every three HOAd1 molecules was reduced. An X-ray diffraction study of the sodium derivative shows that the complex features two unreduced HOAd1 donors as well as the reduced alkoxide (OAd1), with the Ad1 fragments clustered together on the same side of the NaO3 plane, contrary to steric considerations. This is the first example of an alkali metal reduction of an alcohol that is inhibited from completion due to the formation of the [M(OAd1)(HOAd1)2] complexes, stabilized by London dispersion effects. NMR spectroscopic studies revealed similar structures for the lithium and potassium derivatives. Computational analyses indicate that decisive London dispersion effects in the molecular structure are a consequence of the many C−H⋅⋅⋅H−C interactions between the OAd1 groups.Peer reviewe

Unraveling the Steric Link to Copper Precursor Decomposition: A Multi-Faceted Study for the Printing of Flexible Electronics

The field of printed electronics strives for lower processing temperatures to move toward flexible substrates that have vast potential: from wearable medical devices to animal tagging. Typically, ink formulations are optimized using mass screening and elimination of failures; as such, there are no comprehensive studies on the fundamental chemistry at play. Herein, findings which describe the steric link to decomposition profile: combining density functional theory, crystallography, thermal decomposition, mass spectrometry, and inkjet printing, are reported. Through the reaction of copper(II) formate with excess alkanolamines of varying steric bulk, tris-co-ordinated copper precursor ions: "[CuL3 ]," each with a formate counter-ion (1-3) are isolated and their thermal decomposition mass spectrometry profiles are collected to assess their suitability for use in inks (I1-3 ). Spin coating and inkjet printing of I1,2 provides an easily up-scalable method toward the deposition of highly conductive copper device interconnects (ρ = 4.7-5.3 × 10-7 Ω m; ≈30% bulk) onto paper and polyimide substrates and forms functioning circuits that can power light-emitting diodes. The connection among ligand bulk, coordination number, and improved decomposition profile supports fundamental understanding which will direct future design

Terpene Dispersion Energy Donor Ligands in Borane Complexes

Structural characterization of the complex [B(beta-pinane)(3)] (1) reveals non-covalent H center dot center dot center dot H contacts that are consistent with the generation of London dispersion energies involving the beta-pinane ligand frameworks. The homolytic fragmentations of 1, and camphane and sabinane analogues ([B(camphane)(3)] (2) and [B(sabinane)(3)] (3)) were studied computationally. Isodesmic exchange results showed that London dispersion interactions are highly dependent on the terpene's stereochemistry, with the beta-pinane framework providing the greatest dispersion free energy (Delta G = -7.9 kcal mol(-1)) with Grimme's dispersion correction (D3BJ) employed. PMe3 was used to coordinate to [B(beta-pinane)(3)], giving the complex [Me3P-B(beta-pinane)(3)] (4), which displayed a dynamic coordination equilibrium in solution. The association process was found to be slightly endergonic at 302 K (Delta G = +0.29 kcal mol(-1)).Peer reviewe

Molecular Complexes Featuring Unsupported Dispersion-Enhanced Aluminum–Copper and Gallium–Copper Bonds

The reaction of the copper(I) β-diketiminate copper complex {(Cu(BDIMes))2(μ-C6H6)} (BDIMes = N,N′-bis(2,4,6-trimethylphenyl)pentane-2,4-diiminate) with the low-valent group 13 metal β-diketiminates M(BDIDip) (M = Al or Ga; BDIDip = N,N′-bis(2,6-diisopropylphenyl)pentane-2,4-diiminate) in toluene afforded the complexes {(BDIMes)CuAl(BDIDip)} and {(BDIMes)CuGa(BDIDip)}. These feature unsupported copper–aluminum or copper–gallium bonds with short metal–metal distances, Cu–Al = 2.3010(6) Å and Cu–Ga = 2.2916(5) Å. Density functional theory (DFT) calculations showed that approximately half of the calculated association enthalpies can be attributed to London dispersion forces.peerReviewe