EDA-NOCV Analysis of Donor-Base-Stabilized Elusive Monomeric Aluminum Phosphides [(L)P-Al(L'); L, L' = cAAC(Me), NHC(Me), PMe(3)]

供体碱稳定化难以捉摸的单体磷酸铝[(L)P-Al(L'); L, L' = cAAC(Me), NHC(Me), PMe(3)]的EDA-NOCV分析

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Abstract

Herein, we report on the stability and bonding analysis of donor-base-stabilized monomeric AlP species (1-6) of the general formula (L)P-Al(L'); [L = cAAC(Me), L' = cAAC(Me), NHC(Me), PMe(3), (N (i) Pr(2))(2) (1-4); L = L' = NHC(Me), PMe(3) (5 and 6); cAAC = cyclic alkyl(amino) carbene; NHC = N-heterocyclic carbene]. Energy decomposition analysis coupled with natural orbitals for chemical valence (EDA-NOCV) analysis indicates the synthetic viability of this class of species, stabilized in their singlet ground state, in the laboratory. The C(L)-P bond is found to be a partial double bond (WBI ∼ 1.45), while the C(L)/P(L)-Al bond is a single bond (WBI ∼ 0.42-0.69). These bonds are mostly covalent or dative σ/π bonds depending upon the ligands attached. The central P-Al bond is an electron-sharing covalent polar single bond (WBI ∼ 0.80; P-Al) for 1-4 and a dative σ bond for 5 and 6 (WBI ∼ 0.89-0.93; P-Al). The calculated intrinsic interaction energies of the central P-Al bonds are found to be in the range from -116 to -216 kcal/mol (1-3 and 5 and 6). This value is the highest for compound 3, possibly due to the push and pull effects from the ligands PMe(3) and cAAC, respectively.

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