Self‐cross‐linkable ferrocenyl‐containing polymethylhydrosiloxanes were synthesized. Karstedt's catalyst and cis‐[PtCl2(BnCN)2] were examined as cross‐linking catalysts at room temperature for the reaction between Si–H groups of the ferrocenyl‐containing polymethylhydrosiloxanes. Cis‐[PtCl2(BnCN)2] is an effective catalyst that allows cross‐linked ferrocenyl‐containing silicones (silicone rubbers) to be obtained with no visible mechanical defects (bubbles or cracks) compared with Karstedt's catalyst. The ferrocene content of the ferrocenyl‐containing silicone rubbers was found to be approximately 50 wt.% by energy‐dispersive X‐ray analysis. Compared with cross‐linked non‐modified polymethylhydrosiloxanes, the ferrocenyl‐containing silicone rubbers exhibited improved tensile properties (the tensile strength increased from 0.47 to 0.75 MPa) and a 1.5–2.5 times lower cross‐linking degree. The surface resistivity of the ferrocenyl‐containing silicone rubbers (50 wt.% ferrocenyl units) was approximately 7 × 109 Ω/□, which was 10,000 times lower than that of pure polymethylhydrosiloxane. The obtained flexible electroactive ferrocenyl‐containing silicone rubbers can potentially be applied as coatings for electronic and electrostatic‐sensitive devices, interfaces, and sensors.

The platinum-catalyzed self cross-linking of polymethylhydrosiloxane at RT in air was performed for the first time. cis-[PtCl2(BnCN)2] allows creating high-quality silicone rubbers without visible mechanical defects.