biostudies-literatureSinclair MJGEuropean Research CouncilEUTOPIA allianceVrije Universiteit BrusselRoyal SocietyEngineering and Physical Sciences Research Council1709-1713https://www.ebi.ac.uk/biostudies/studies/S-EPMC10828984biostudies-literatureUnknown63(4)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 = <i>t</i>Bu, 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 moInorganic chemistryT-Shaped Palladium and Platinum {MNO}¹⁰ Nitrosyl Complexes.PMC10828984co-tutelle studentship to N.R.637313DTP studentship to M.J.G.S.UF150675UF100592Tsoureas NGyton MRRoig NChaplin ABAlonso MSinclair MJGCloke FGNfalseT-Shaped Palladium and Platinum {MNO}¹⁰ Nitrosyl Complexes.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 = <i>t</i>Bu, 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 mo2024-01-01T00:00:00Z2024 Jan2025-04-26T10:28:37.51Z2025-04-06T13:24:27.636ZS-EPMC108289843820721210.1021/acs.inorgchem.3c03434