T-Shaped Palladium and Platinum {MNO}10 Nitrosyl Complexes

Matthew J G Sinclair; Nil Roig; Matthew R Gyton; Nikolaos Tsoureas; F Geoffrey N Cloke; Mercedes Alonso; Adrian B Chaplin

doi:10.1021/acs.inorgchem.3c03434

T-Shaped Palladium and Platinum {MNO}¹⁰ Nitrosyl Complexes

Inorg Chem. 2024 Jan 29;63(4):1709-1713. doi: 10.1021/acs.inorgchem.3c03434. Epub 2024 Jan 11.

Authors

Matthew J G Sinclair¹, Nil Roig^{1

2}, Matthew R Gyton¹, Nikolaos Tsoureas³, F Geoffrey N Cloke³, Mercedes Alonso², Adrian B Chaplin¹

Affiliations

¹ Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, U.K.
² Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel (VUB), 1050 Brussels, Belgium.
³ Department of Chemistry, University of Sussex, Falmer, Brighton BN1 9QR, U.K.

Abstract

The synthesis and characterization of a homologous series of T-shaped {MNO}¹⁰ nitrosyl complexes of the form [M(PR₃)₂(NO)]⁺ (M = Pd, Pt; R = tBu, Ad) are reported. These diamagnetic nitrosyls are obtained from monovalent or zerovalent precursors by treatment with NO and NO⁺, respectively, and are notable for distinctly bent M-NO angles of ∼123° in the solid state. Adoption of this coordination mode in solution is also supported by the analysis of isotopically enriched samples by ¹⁵N NMR spectroscopy. Effective oxidation states of M⁰/NO⁺ are calculated, and metal-nitrosyl bonding has been interrogated using DFT-based energy decomposition analysis techniques. While a linear nitrosyl coordination mode was found to be electronically preferred, the M-NO and P-M-P angles are inversely correlated to the extent that binding in this manner is prevented by steric repulsion between the bulky ancillary phosphine ligands.