“…Another class of photoactivatable platinum catalysts contains dicarbonyl ligands derived from acetyl acetone such as dimeric trimethyl(ˇ-dicarbonyl)Pt(IV) complexes of the general formula type [Me 3 Pt(RC(O)CHC(O)R)] 2 (R = Me, OEt, Ph, CF 3 ) which can be activated by irradiation of 225-260 nm [188]. These complexes show similar reactivities to CpPtMe 3 and are more active than Pt(acac) 2 (acac = acetylacetone).…”
“…Another class of photoactivatable platinum catalysts contains dicarbonyl ligands derived from acetyl acetone such as dimeric trimethyl(ˇ-dicarbonyl)Pt(IV) complexes of the general formula type [Me 3 Pt(RC(O)CHC(O)R)] 2 (R = Me, OEt, Ph, CF 3 ) which can be activated by irradiation of 225-260 nm [188]. These complexes show similar reactivities to CpPtMe 3 and are more active than Pt(acac) 2 (acac = acetylacetone).…”
“…Fouassier and coworkers employed various β-dicarbonyl-Pt IV R 3 complexes ( Figure 31 ) as useful photoinitators for hydrosilylation reaction of silicone polymers containing Si–H/Si–vinyl and Si–H/Si–epoxide moieties [ 83 ]. During photolysis of the initiator, colloidal platinum was generated.…”
Section: Non-thermal Stimuli For Hydrosilylation Reactionsmentioning
Hydrosilylation reactions, the (commonly) anti-Markovnikov additions of silanes to unsaturated bonds present in compounds such as alkenes and alkynes, offer numerous unique and advantageous properties for the preparation of polymeric materials, such as high yields and stereoselectivity. These reactions require to be catalyzed, for which platinum compounds were used in the initial stages. Celebrating the 50th anniversary of hydrosilylations in polymer science and, concomitantly, five decades of continuously growing research, hydrosilylation reactions have advanced to a level that renders them predestined for transfer into commercial products on the large scale. Facing this potential transfer, this review addresses and discusses selected current trends of the scientific research in the area, namely low-cost transition metal catalysts (focusing on iron, cobalt, and nickel complexes), metal-free catalysts, non-thermally triggered hydrosilylation reactions (highlighting stimuli such as (UV-)light), and (potential) industrial applications (highlighting the catalysts used and products manufactured). This review focuses on the hydrosilylation reactions involving alkene reactants.
“…The secondary photoproduct mediates hydrosilation to yield the cross-linked products. A similar process was recently postulated for photoactivated hydrosilation of silicone polymers with trialkyl(β-dicarbonyl) platinum(IV) complexes. , 1 Photoactivation of Pt(L) 2 Complexes in the Presence of the OMSM and TVS for Hydrosilation Cross-Linking …”
Three platinum(II) bis(β-diketonate) complexes are highly active for photocatalytic hydrosilation cross-linking of oligo[(methylsilylene)methylene] with tetravinylsilane. Platinum(II) bis(benzoylacetonate), platinum(II) bis(trifluoroacetylacetonate), and platinum(II) bis(benzoyltrifluoroacetonate) are photoactivated by visible light for catalysis, while platinum(II) bis(hexafluoroacetylacetonate) can be used as a thermal catalyst. Kinetic data from FT-IR and UV-visible spectroscopies characterizing Si-H bond conversion and catalyst photolysis are reported.
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