Is silicone straight out of the canister resistant to electricity ?

Do you mean silicone sealant or silicone grease?
If you are using sealant you want to use neutral cure silicone. The ordinary silicone contains acetic acid that smells like vinegar and might cause problems.
You don't say how far underwater you want to immerse the connections but you could always pot them inside a small plastic box for extra protection.
 
This probably will not answer your question.

I had need to carry an SSB and was not willing to invest in an insulated backstay. I bought two shackle kits, composedd of 2 shackles separated by a 'plastic' washer (the washer looked like a small sheave). These are standard components to insulate stainless lifeline (the things through your stanchions). I used these paired shackles at the top and bottom of our then backstay and filled the device full of transparent silicone, that cured with acerbic acid, nothing fancy. They worked a treat. I did 2 China sea races with this assembly, rain and shine, and the backstay was used maybe 150 times between the 2 China Sea races.

But you say you want to use your assembly 'straight away' - silicone takes time to set off.

I am having made, Granddaughter is half way through assembly, an accelerometer to measure movement on a yacht, under water (don't ask!). We intend packing in a 'click clack' plastic box with silicon seals and fill the box with oil and then pack the whole in a further box. To be used at 5m depths. The device will be self contained, re-chargeable power source and a data card.

Jonathan
 
I'd use contralube and then pot over it but I am unusual and I like a job to last100 years. Contralube shows up with uv light iirc
 
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