Thanks everyone for the suggestions (& sorry I couldn't reply earlier - internet died yesterday arvo

). I'll check them all out to see what specs / packages / availability suit best. For some reason I forgot the LM358 went down that far - I should've checked the datasheet before posting...
As for your particular case, since you already have so much voltage swing, why not just divide it against 0V and live with the offset? It's not like you're losing many bits -- or that you (evidently) care about many bits to begin with (the internal ADC is 10 bit with some 4 LSBs of INL/DNL error -- if you require absolute, uncalibrated accuracy, it's more like 8 bits anyway).
Or you could just divide the voltage by two (and you'll have 0.75-3.2v) and use a better adc ...
True, and I'm using a divider at the moment. In this case I'm less concerned with accuracy/repeatability (beyond knowing where the middle and ends of the pot rotation are) than resolution, and using a divider essentially throws away ~20% of what little useful resolution there is. Between that, dealing with the ADC quality, & including a small dead-band around the pot's centre rotation (to aid tuning), the resulting fine tuning of the digital VFO is just a
little too "step-like" and digital.
I've tested it with a 0-5v divider pot and the extra resolution I gain from going all the way down to 0v is enough to make things feel suitably analogue. However, this is designed to hook up to existing expansion connectors in an existing receiver, and I'd rather not mod the receiver to change the fine tune signal from 1.5-6.5v to 0-5v. Hence the need for a suitable op-amp...
Not worth using an op-amp as comparator, certainly not at 5MHz ... Or you can simply use a couple 2N3904s. 
Yeah, you really don't want to see what I'm using in my breadboarded proof-of-concept. Hint: why use "a couple of 2N3904s" when a single BC548 works
j-u-s-t well enough?

Never "abuse" an OpAmp as comparator. The schematic symbol is the same and maybe the input stage is similar, but the rest is not. Use a comparator to to a comparators job.
Yup, well aware that it's not the done thing, and I even know why - but I'd hardly be the first to do it, would I?
Point taken though; I'll use a couple of suitable transistors. I need one anyway for a low-impedance driver on the VFO output.
Again, thanks all!