Structural variety in silver alkoxide complexes supported by neutral phosphorus-, nitrogen-, and carbon-donor ligands
Related Experiment Video
Updated: Nov 4, 2026

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Nicholas A Hoffman1, Christina K McCabe1, Andrew Niles L Ocampochua1
1Department of Chemistry, McMaster University, 1280 Main St. West, Hamilton, Ontario, L8S 4M1, Canada. emslied@mcmaster.ca.
Abstract:
Silver perfluoro-tert-butoxide complexes were synthesized bearing phosphinite, aminophosphine, isonitrile, pyridine, bis(amine), bis(phosphine), and mixed phosphine/amine ligands: [(Ag{μ-OC(CF3)3}{L})2] {L = PiPr2(OMe) (1), PiPr2(OtBu) (2), PiPr2(NMe2) (3)}, [(Ag{μ-OC(CF3)3}{CNR})n] {R = Me (n = 2; 4) or tBu (n = 4; 5)}, [(Ag{μ-OC(CF3)3}{py})2] (6), [(Ag{μ-OC(CF3)3}{κ2-tmeda})2] (7), [(Ag{OC(CF3)3}{μ-Me2P(CH2)nPMe2})2] {n = 1 (8) or 2 (9)}, and polymeric [(Ag{OC(CF3)3}{μ-iPr2P(CH2)2NMe2})n] (10). In the solid state, 1-4 and 6 and 7 are dimers with bridging alkoxide ligands. In contrast, the tert-butyl-isonitrile complex (5) is a tetramer with a cubic Ag4O4 core, the dmpm and dmpe (8 and 9) complexes are dimers with terminal alkoxide groups and bridging bis(phosphine) ligands, and 10 is polymeric with bridging iPr2P(CH2)2NMe2 ligands. In solution, 8 retains the dimeric structure, with the 107Ag/109Ag isotopologue giving rise to a complex 31P{1H} NMR spectrum at low temperature due to second-order effects, whereas 9 exists as a temperature-dependent mixture of oligomers. The solid-state structures of selected compounds were further investigated through Hirshfeld surface and interaction energy calculations. The volatility and thermal stability of 1-10 were evaluated to probe their potential as precursors for Atomic Layer Deposition (ALD). Compounds 1-5 and 10 sublimed cleanly at 5 mTorr between 50 and 100 °C, whereas 6-9 underwent partial or complete decomposition upon attempted sublimation. The PiPr2(OtBu) complex (2) has the highest volatility of 1-10, combined with a low melting point, but thermogravimetric analysis (TGA) revealed competing decomposition and volatilization pathways under the conditions of the measurement.
More Related Videos
10:51The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
07:20Discovery and Synthesis Optimization of Isoreticular Al(III) Phosphonate-Based Metal-Organic Framework Compounds Using High-Throughput Methods
Published on: October 6, 2023
Related Concept Videos
Metal-Ligand Bonds
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
Structural Isomerism
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
Coordination Compounds and Nomenclature
Valence Bond Theory
Complexation Equilibria: Factors Influencing Stability of Complexes
Chirality at Nitrogen, Phosphorus, and Sulfur
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...