The Stability of Diphosphino-Boryl PBP Pincer Backbone: PBP to POP Ligand Hydrolysis

Since moisture may frequently be present in many solvents, it is important to know the reactivity of a catalyst against water for catalytic reactions. In order to explore the stability and understand the transformation process of diphosphino-boryl-based PBP pincer platform, [PdCl{B(NCH₂ P^t Bu₂ )₂ -o-C₆ H₄ }] (1) was treated with PdCl₂ , HB(NCH₂ PPh₂ )₂ -o-C₆ H₄ was reacted with [PdCl₂ (cod)] (cod=cyclo-octa-1,5-diene) and [Pd₂ (dba)₃ ] (dba=dibenzylideneacetone), respectively, in the presence of water. Some novel palladium POP complexes, [Pd₂ Cl₂ (μ-Cl){μ-κ³ -P,O,P-OB(NCH₂ P^t Bu₂ )₂ -o-C₆ H₄ }] (2 a), [Pd₄ (μ-Cl)₂ (μ-O)₂ {μ-κ³ -P,O,P-OB(NCH₂ PPh₂ )₂ -o-C₆ H₄ }₂ ] (2 b), [Pd₂ {μ-κ⁴ -P,P,P,P-O(B(NCH₂ PPh₂ )₂ -o-C₆ H₄ )₂ }{μ-κ² -P,P-(NHCH₂ PPh₂ )₂ -o-C₆ H₄ }] (3), were obtained. It was found that the PBP pincer backbone can easily be converted into a POP backbone in the presence of water. From the crystal structures of the resultant palladium complexes, possible pincer backbone transformation pathways were discussed.