# Regioselective Hydrosilylation Catalysis with Supported Well-Defined Pt(0) Complexes: Effects of Surface Anions and Phosphenium Ligands

## TL;DR

Scientists created stable, selective catalysts using platinum and surface-bound ligands, achieving high performance in chemical reactions.

## Contribution

The study introduces a new method for creating selective single-atom catalysts using surface-bound phosphenium ligands and Pt(0) complexes.

## Key findings

- Bulky aromatic ligands improve regioselectivity in hydrosilylation reactions.
- Stronger-coordinating anions enhance the selectivity of the precatalysts.
- Surface-bound Pt(0) complexes perform comparably to molecular Pt catalysts.

## Abstract

Achieving stable, selective single-atom catalysts is
challenging
because localsurface-site structures are difficult to control. Surface
organometallic chemistry and organic–inorganic hybrid materials
offer partial solutions, but applications to supporting zero-valent
metals are limited. We demonstrate that well-defined, ionically bound
N-heterocyclic phosphenium ([NHP]+) ligands can be generated
on silylium-functionalized sulfated zirconia ([iPr3Si]­[SZO]). These surface-bound [NHP]­[SZO] ligands coordinate
Pt(0) centers, forming [(NHP)­Pt(0)­L]­[SZO] precatalysts that are highly
active for alkyne hydrosilylation. Systematic studies reveal that
sterically bulky aromatic ligands enhance regio­selectivity,
achieving performances comparable to molecular Pt catalysts. Further,
more-coordinating anions support more-regio­selective precatalysts;
therefore, SZO supports more-selective species than weaker-coordinating
Al­(OC­(CF3)3)3-functionalized silica,
a trend confirmed by molecular analogues. These results demonstrate
that both the ligand and support control catalytic behavior and enable
solid-state structure–activity relationships.