Personally I do it as part of the RAW file conversion as this gives the greatest flexibility and control. The changes you want for colour are sometimes very different to the ones you want for mono, hence making the decision early.
I've always found it varies from image to image, as well as the method used to convert it to B&W. Sometimes I've produced two images using different B&W conversion methods then composited them (or various parts of each using layer masks).
There's really no right or wrong, just what works for you.
If you are intending to use the image as B&W I would suggest it's one of the first things to do. Only in B&W will you see what the final result is, no point in doing a lot of complex PP only to find it stands out like a sore thumb when converted.
What does the final image look like in your head? Where you convert depends on the result you want to end up with.
If it's a simple image you just want in mono then I would do it first since any other processing you do might affect the contrast and levels etc. If you're using mono as a special artisitc effect then you are best to duplicate the original image and convert the duplicate then work with layers.
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