How do you apply the silicon to the connectors? Do you plug them in and then smear it over them?
I'm not sure what the electrical benefit would be for doing that. The wires and plugs are already insulated. Unless you have a lot of electrical storms, keep a Tesla coil around or like to rub the cables with a wool sweater, the insulation will perform just fine.
Don't worry about static electricity. If it's there, it's not going to affect the sound. A bigger worry should be how sunspot cycles change the amount of RF reflected off the ionosphere. Unshielded cables do pick up RF. But that's not that big of a deal, either, unless your ham neighbor is tuning up on 40m and you start hearing his voice in your rig.
Nevertheless, the only use I'd see for the silicon would be to prevent corrosion on the connectors. Unless you live in a damp climate, don't worry about it.