In your sentence, the word "most" is synonymous with "very" and it functions as an adverb modifying the word "probably". Adverbs can be used to modify verbs, adjectives and also other adverbs . The combination "most probably" is grammatically OK.
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CalifJim but likable rapport strikes me as pretty strange too.Me, too. A collocation such as "easy rapport" would sound more typical to me.