Nickel and Palladium Allyl‐Triazenide Precursors for the Generation of Supported Nanoparticles

Abstract 1,3‐Dialkyltriazenides are isolobal to amidinates, and both ligands are popular in atomic layer deposition. Given our recent success with the N,N’ ‐diisopropylacetamidinate (DIA) ligand in surface organometallic chemistry, we investigated the 1,3‐ tert ‐butyltriazenide (DTZ) ligand to stabilize Ni‐ and Pd‐allyl complexes for the generation of supported nanoparticles. Using the analogous synthetic pathway employed for allyl‐amidinate complexes, the formation of dinuclear structures was obtained, where two triazenide ligands bridge the metal centers. Grafting on SiO 2‐700 was almost quantitative for {Ni(η 3 ‐allyl)(µ‐DTZ)} 2 while only partial for {Pd(η 3 ‐allyl)(µ‐DTZ)} 2 (ca. 50%), contrasting what was observed for the corresponding amidinate derivatives that grafted almost quantitatively for both Ni and Pd. Heat treatment of the grafted materials under a flow of H 2 yielded supported nanoparticles (Ni: 1.1 nm, Pd: 1.3 nm) that were significantly smaller than those obtained with the respective amidinate complexes and feature very narrow size distribution (standard deviation σ = 0.2 nm for Ni, 0.3 nm for Pd). Hence, the presented complexes are viable precursors for the generation of small and narrowly dispersed supported nanoparticles.