Snapshots of the AlAl σ‐Bond Formation Starting from {AlR₂} Units: Experimental and Computational Observations

Abstract

The approach of two atoms with an unpaired electron each results in the formation of a σ bond. Snapshots of the primary step with a large atom‐to‐atom distance and a parallel spin of both electrons and of the final product, consisting of a butterfly structure with a short AlAl σ bond, have been identified for a [R2PAl(PR2)AlPR2] compound using quantum chemical calculations and X‐ray crystallography (see scheme).

K[Al4(PPh2)7PPh]: An AlII Phosphanide / Phosphinidene Intermediate on the Path to AlP Formation

“…[9,11] Although the alkyl substituent of the phosphanides differs, the Al/P frameworks in all three compounds have notably similarities in Al-P coordination and metric parameters. These structures are shown in the SI.…”

“…[9][10][11] The latter complex contains a naked P 3-ion that presumably results from a successive ligand-based decomposition process leading to the Al 3 P moiety. DFT studies showed how the ligand redox vs. disproportionation pathways followed different routes from the Al I precursors to give markedly different products.…”

N‐Heterocyclic Vinylidene‐Stabilized Phosphorus Biradicaloid

“…In 2002, Bertrand and co‐workers reported a zwitterionic compound ( B ) featuring a B 2 P 2 ring. Later, Schnöckel et al . prepared an aluminum analogue with a Al 2 P 2 ring ( C ).…”

VIBRATIONAL SCALING FACTORS FOR Rh(I) CARBONYL COMPOUNDS IN HOMOGENEOUS CATALYSIS

“…For all atomic orbitals, the def2-TZVP basis set was used [20] substituting previous Ahlrichs' basis sets [21]. This basis set was shown to give reliable vibrational CO frequencies for a number of metal complexes, see for example [22][23][24]. All final structures were characterized to be minima by calculating the Hessian matrices at the respective level and the absence of any imaginary eigenvalues.…”