Coordination mode and stability of the tetrahydroborate ligand in group 10 metal pincer complexes

Abstract

The coordination mode of the BH₄⁻ ligand in transition metal tetrahydroborate complexes is mainly dominated by the nature of the metal centres. However, other factors can also play important roles sometimes. In order to rationalize the coordination modes and the stability of the BH₄⁻ ligand in group 10 metal tetrahydroborate pincer complexes, [2,6-(^tBu₂PO)₂C₆H₃]Pt(η¹-HBH₃) and [C₆H₄-o-(NCH₂P^tBu₂)₂B]M(η²-H₂BH₂) (M = Ni, Pt) were prepared and characterized. A structural comparison of [2,6-(^tBu₂PCH₂)₂C₆H₃]Ni(BH₄), [2,6-(^tBu₂PO)₂C₆H₃]M(BH₄) and [C₆H₄-o-(NCH₂P^tBu₂)₂B]M(BH₄) (M = Ni, Pd, and Pt) indicates that the M–P bond length, the P–M–P bite angle and the trans-influence of the central atom in the pincer platform also affect the coordination mode of the BH₄⁻ ligand. The nickel complexes tend to adopt a monodentate coordination mode while the palladium and platinum complexes can adopt either the monodentate or the bidentate mode depending on the structural features of the pincer platforms. Longer M–P bonds and smaller P–M–P bite angles favour the bidentate mode. The stability of the BH₄⁻ ligand is influenced by both the coordination mode and the nature of the metal centre. The BH₃ species is released more easily from complexes with less electron rich metal centres. Following the series of Ni, Pd, and Pt, complexes with the same pincer ligand more easily lose a BH₃ moiety.