Abstract
A library of platinum (II) complexes of general formula (O,O′-β-diketonate)PtLX (L = dimethylsulfoxide, pyridine, triphenylphosphine; X = chloride, γ-acetylacetonate) has been prepared, using synthetic methodologies available in the literature. The library has been supplemented with a novel platinum (II) complex bearing a triazenido N-oxide ligand. The complexes have been characterized and tested as precatalysts for the photoactivated curing of silicone resins. Correlations have been established between the nature of the employed ligands, the ultraviolet-visible (UV-Vis) absorption spectrum of the complexes and their catalytic performance, which enable the tailored preparation of complexes with improved performance in view of possible technological applications.
Highlights
The hydrosilylation reaction of unsaturated organic moieties, C=C double bonds, is a well-established synthetic methodology with extensive applications both in the academy and the industry [1,2]
The reaction can serve in the production of low molecular weight organosilicon compounds with applications as chemical intermediates, and in the manufacturing, chemical modification and crosslinking of silicone polymers [3,4]
Beside the more traditional thermally activated curing, research in this field has lately focused on photoactivated curing, since the mild reaction conditions that can be maintained using photoactivation enable the extension of the applicability of silicone resins to fields such as dentistry [5]
Summary
The hydrosilylation reaction of unsaturated organic moieties, C=C double bonds, is a well-established synthetic methodology with extensive applications both in the academy and the industry [1,2]. Critical for success appears to be the absence of ligands L with a soft character and strong σ-donating properties, which are detrimental for catalyst activity at room temperature, as well as the use of a β-diketonate ligand building up with the platinum (II) center a metallacyclic system with a more extensive electron delocalization, which shifts the absorption of the complex towards the visible range and enables a more efficient photoactivation In this respect, complexes with chloride as the X ligand exhibit an absorption spectrum shifted slightly more towards higher wavelengths compared with complexes in which γ-acac is the X ligand, and appear better suited for the scope. Work aimed at the rational use of inhibitors in this context is currently underway
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