Activation of the Ga<sup>I</sup> Cation for Bond Activation: from Oxidative Additions into C−Cl and H−P Bonds to Reversible Insertion into P<sub>4</sub>
Philipp Dabringhaus, Tim Heizmann, Ingo Krossing
Abstract
Abstract Although the discovery of the Ga I complex salt [Ga(PhF) 2‐3 ][Al(OR F ) 4 ] (R F =C(CF 3 ) 3 , PhF=C 6 H 5 F) invoked the preparation of a diverse library of cationic Ga(I) coordination complexes and clusters, studies on small molecule activation with low‐valent Ga I cations are scarce. Herein, a first experimental study on the reactivity of a monomeric Ga(I) cation activated with a pyridine–diimine pincer ligand (in [Ga(PDI dipp )][Al(OR F ) 4 ]) towards small‐molecules is reported. First controlled oxidative additions of the Ga I cation into C−Cl, H−P and P−P bonds are presented. Moreover, the [4+1]cycloaddition to butadienes was achieved. Intriguingly, the isolated, blue insertion product into the P−P bond of P 4 allows for the quantitative release of the P 4 molecule upon reaction with AlEt 3 and butadienes. Reversible P 4 insertion of main‐group metals has previously been reported for Ge and Sn, respectively. The experimental study is supported by high‐level computational analysis of the in‐part reversible oxidative additions at the DLPNO‐CCSD(T)/def2‐TZVPP//PBEh‐3c/def2‐mSVP level of theory with COSMO‐RS solvation in 1,2‐difluorobenzene.