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Often assumed to come from the zero-grade. However there are no secure examples of *n̥ > Balto-Slavic *un (other examples like *sъto (often considered to be an Iranian borrowing) are all riddled with difficulties and unreliable), and the o-grade *h₁ón can be posited instead. See also *mъnogъ, *vъnukъ, *vъnъ, *vъtorъ and *kъ(n), *gъnati, *gъrnъ, *gъrdlo, *kъrma, *dǫti/*dъmǫ.
Because of the law of open syllables, the final -n was normally dropped. But when combined with a stem that (originally?) began with a vowel, it was attached to the following word. (Example: *vъn *jejь > Bulgarianвнея "in her").
Derksen, Rick (2008) “*vъ(n)”, in Etymological Dictionary of the Slavic Inherited Lexicon (Leiden Indo-European Etymological Dictionary Series; 4), Leiden, Boston: Brill, →ISBN, →ISSN, page 530
Anikin, A. E. (2011) “в, во”, in Русский этимологический словарь [Russian Etymological Dictionary] (in Russian), numbers 5 (буба – вакштаф), Moscow: Znak, →ISBN, page 304
Vasmer, Max (1964–1973) “в”, in Oleg Trubachyov, transl., Этимологический словарь русского языка [Etymological Dictionary of the Russian Language] (in Russian), Moscow: Progress