2025/01/24 by Matthew J. G. Sinclair, Nil Roig, Nikolaos Tsoureas +2 · 1 voice
Materials Science · Chemistry · #Lanthanide and Transition Metal Complexes #Organometallic Complex Synthesis and Catalysis #Magnetism in coordination complexes
paper · pdf · doi:10.1002/ejic.202400803
openalex publication_date 2025/01/24 · openalex created_date 2025/01/25 · openalex updated_date 2026/07/31
Abstract The synthesis and characterisation of two square planar PdNO 10 pincer complexes of the form [Pd(pincer)(NO)] + (pincer = 2,6‐( t Bu 2 PCH 2 ) 2 C 5 H 3 N, 1 ; 2,6‐( t Bu 2 PO) 2 C 5 H 3 N, 2 ) are reported. These complexes are readily isolated by phosphine substitution of T‐shaped [Pd(P t Bu 3 ) 2 (NO)] + 3 in THF and the bent nitrosyl coordination mode observed in 3 is retained, as evidenced by X‐ray diffraction (∠PdNO ∼ 120°), IR spectroscopy and analysis of isotopically enriched samples by 15 N NMR spectroscopy. Effective oxidation states of Pd 0 /NO + are calculated for 1 – 3 and nitrosyl coordination is principally attributed to metal‐centred σ ‐bonding, with supplementary π ‐backbonding. Computational analysis, however, indicates that the Pd−NO bonds in 1 and 2 have greater Pd I /NO • character and σ ‐bonding is more prominent than in 3 . These differences in bonding are manifested experimentally in more red‐shifted nitrosyl stretching frequencies and the propensity of 1 and 2 to react with dichloromethane to afford palladium(II) chloride derivatives.