Steric and Electronic Effect of Cp-Substituents on the Structure of the Ruthenocene Based Pincer Palladium Borohydrides

Ruthenocene-based PCP^tBu pincer ligands were used to synthesize novel pincer palladium chloride Rc^F[PCP^tBu]PdCl (2a) and two novel palladium tetrahydroborates Rc^F[PCP^tBu]Pd(BH₄) (3a) and Rc^*[PCP^tBu]Pd(BH₄) (3b), where Rc^F[PCP^tBu] = κ³-{2,5-(tBu₂PCH₂)_2-C₅H₂}Ru(Cp^F) (Cp^F = C₅Me₄CF₃), and Rc*[PCP^tBu] = κ³-{2,5-(tBu₂PCH₂)₂C₅H₂}Ru(Cp*) (Cp* = C₅Me₅). These coordination compounds were characterized by X-ray, NMR and FTIR techniques. Analysis of the X-ray data shows that an increase of the steric bulk of non-metalated cyclopentadienyl ring in 3a and 3b relative to non-substituted Rc[PCP^tBu]Pd(BH₄) analogue (3c; where Rc[PCP^tBu] = κ³-{2,5-(tBu₂PCH₂)₂C₅H₂}Ru(Cp), Cp = C₅H₅) pushes palladium atom from the middle plane of the metalated Cp ring in the direction opposite to the ruthenium atom. This displacement increases in the order 3c < 3b < 3a following the order of the Cp-ring steric volume increase. The analysis of both X-ray and IR data suggests that BH₄ ligand in both palladium tetrahydroborates 3a and 3b has the mixed coordination mode η^1,2. The strength of the BH₄ bond with palladium atom increases in the order Rc[PCP^tBu]Pd(BH₄) < Rc*[PCP^tBu]Pd(BH₄) < Rc^F[PCP^tBu]Pd(BH₄) that appears to be affected by both steric and electronic properties of the ruthenocene moiety.