Abstract
The synthesis and characterisation of two square planar {PdNO}10 pincer complexes of the form [Pd(pincer)(NO)]+(pincer = 2,6‐(tBu2PCH2)2C5H3N, 1; 2,6‐(tBu2PO)2C5H3N, 2) are reported. These complexes are readily isolated by phosphine substitution of T‐shaped [Pd(PtBu3)2(NO)]+ 3 in THF and the bent nitrosyl coordination mode observed in 3is retained, as evidenced by X‐ray diffraction (∠PdNO ∼120°), IR spectroscopy and analysis of isotopically enriched samples by 15N NMR spectroscopy. Effective oxidation states of Pd0/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 PdI/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.
Published Version
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