Bonding in PdCl(NO) and Related Nitrosylmetal Species of the Enemark–Feltham {MNO}10Type

Schröder, Daniel und Klüfers, Peter (2023): Bonding in PdCl(NO) and Related Nitrosylmetal Species of the Enemark–Feltham {MNO}10Type. In: Zeitschrift für anorganische und allgemeine Chemie, Bd. 649, Nr. 6-7

Abstract

The crystal-structure analysis of the coordination polymer PdCl(NO) (1) by Evers et al. shows a two-dimensional PdCl network of four-coordinate Pd atoms and triply bridging chlorido ligands. The fourth ligand at Pd is a terminally bonded nitrosyl ligand in a bent PdNO function (Pd−N−O=129°). In terms of the Enemark–Feltham notation, 1 is an {MNO}10 compound which leaves a choice regarding the assignment of the ten electrons as d10-Pd0Cl−(NO+), d9-PdICl−(NO) or d8-PdIICl−(NO−) with 0, 1 and 2 electrons allocated at the nitrosyl ligand, respectively. The quantum-chemical treatment by DFT methods and subsequent determination of the oxidation states (OSs) by Salvador's Effective-OS (EOS) method shows highly covalent Pd−NO bonds which narrowly end up on the Pd0Cl−(NO+) side in the course of the OS assignment's heterolytic bond-cleavage procedure. Related halonitrosyls are included to examine the obvious suitability of both linear and bent MNO units as ‘ground-state canditates’ of {MNO}10 systems. Local-mode analysis confirmed the recently formulated weakening of both the metal−nitrosyl and the N−O bond on bending a linear MNO function.

• Dokumententyp: Zeitschriftenartikel
• Fakultät: Chemie und Pharmazie > Department Chemie
• Themengebiete: 500 Naturwissenschaften und Mathematik > 540 Chemie
• ISSN: 0044-2313
• Sprache: Englisch