Isolation of Elusive Phosphinidene-Chlorotetrylenes: The Heavier Cyanogen Chloride Analogues

The elusive phosphinidene-chlorotetrylenes, [PGeCl] and [PSiCl] have been stabilized by the hetero-bileptic cyclic alkyl(amino) carbene (cAAC), N-heterocyclic carbene (NHC) ligands, and isolated in the solid state at room temperature as the first neutral monomeric species of this class with the general formulae (L)P-ECl(L') (E=Ge, 3 a-3 c; E=Si, 6; L=cAAC; L'=NHC). Compounds 3 a-3 c have been synthesized by the reaction of cAAC-supported potassium phosphinidenides [cAAC=PK(THF)_x ]_n (1 a-1 c) with the adduct NHC:→GeCl₂ (2). Similarly, compound 6 has been synthesized via reaction of 1 a with NHC:→SiCl₂ adduct (4). Compounds 3 a-3 c, and 6 have been structurally characterized by single-crystal X-ray diffraction, NMR spectroscopy and mass spectrometric analysis. DFT calculations revealed that the heteroatom P in 3 bears two lone pairs; the non-bonding pair with 67.8 % of s- and 32 % of p character, whereas the other lone pair is involved in π backdonation to the C_cAAC -N π* of cAAC. The Ge atom in 3 contains a lone pair with 80 % of s character, and slightly involved in the π backdonation to C_NHC . EDA-NOCV analyses showed that two charged doublet fragments {(cAAC)(NHC)}⁺ , and {PGeCl}^- prefer to form one covalent electron-sharing σ bond, one dative σ bond, one dative π bond, and a charge polarized weak π bond. The covalent electron-sharing σ bond contributes to the major stabilization energy to the total orbital interaction energy of 3, enabling the first successful isolations of this class of compounds (3, 6) in the laboratory.