IrI(η4-diene) precatalyst activation by strong bases: formation of an anionic IrIII tetrahydride

The reaction between [IrCl(COD)](2) and dppe in a 1 : 2 ratio was investigated in detail under three different conditions. [IrCl(COD)(dppe)], 1, is formed at room temperature in the absence of base. In the presence of a strong base at room temperature, hydride complexes that retain the carbocyclic ligand in the coordination sphere are generated. In isopropanol, 1 is converted into [IrH(1,2,5,6-eta(2):eta(2)-COD)(dppe)] (2) on addition of (KOBu)-Bu-t, with k(12) = (1.11 +/- 0.02) x 10(-4) s(-1), followed by reversible isomerisation to [IrH(1-kappa-4,5,6-eta(3)-C8H12)(dppe)] (3) with k(23) = (3.4 +/- 0.2) x 10(-4) s(-1) and k(32) = (1.1 +/- 0.3) x 10(-5) s(-1) to yield an equilibrium 5 : 95 mixture of 2 and 3. However, when no hydride source is present in the strong base ((KOBu)-Bu-t in benzene or toluene), the COD ligand in 1 is deprotonated, followed by beta-H elimination of an Ir-I-C8H11 intermediate, which leads to complex [IrH(1-kappa-4,5,6-eta(3)-C8H10)(dppe)] (4) selectively. This is followed by its reversible isomerisation to 5, which features a different relative orientation of the same ligands (k(45) = (3.92 +/- 0.11) x 10(-4) s(-1); k(5-4) = (1.39 +/- 0.12) x 10(-4) s(-1) in C6D6), to yield an equilibrated 32 : 68 mixture of 4 and 5. DFT calculations assisted in the full rationalization of the selectivity and mechanism of the reactions, yielding thermodynamic (equilibrium) and kinetic (isomerization barriers) parameters in excellent agreement with the experimental values. Finally, in the presence of (KOBu)-Bu-t and isopropanol at 80 ?, 1 is transformed selectively to K[IrH4(dppe)] (6), a salt of an anionic tetrahydride complex of Ir-III. This product is also selectively generated from 2, 3, 4 and 5 and H-2 at room temperature, but only when a strong base is present. These results provide an insight into the catalytic action of [IrCl(COD)(LL)] complexes in the hydrogenation of polar substrates in the presence of a base.

Automated summary

The reaction between [IrCl(COD)](2) and dppe in a 1 : 2 ratio was studied under different conditions. The formation of [IrCl(COD)(dppe)], 1, was observed at room temperature without base. In the presence of a strong base, hydride complexes and deprotonation reactions were observed, leading to the formation of various complexes such as [IrH(1,2,5,6-eta(2):eta(2)-COD)(dppe)], [IrH(1-kappa-4,5,6-eta(3)-C8H12)(dppe)], and [IrH(1-kappa-4,5,6-eta(3)-C8H10)(dppe)]. The selectivity and mechanism of these reactions were explained using DFT calculations.