I'm afraid this is not possible (and even in Visual Studio 2012 I don't get tooltips for statements).
I suppose this can be implemented, but as you say, operators usually have simple types. When using custom operators, they should probably be simple enough so that people can use them without looking at their type (or the corresponding XML documentation). Otherwise, it would be better to use a named function.
However, if you use F # Interactive, then you can easily use this to learn the type of operator:
> (!><);; val it : ('a -> unit) = <fun: clo@2 >
If I cannot use F # Interactive, I usually define a simple dummy character to get IntelliSense:
let dummy () = (!><)
Notice that I added the unit argument to define the function and avoid the value limitation error.
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