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The studies apprehended the requirements for Mn(I) complexes to be active in both asymmetric direct (<jats:bold>AH<\/jats:bold>) and transfer hydrogenations (<jats:bold>ATH<\/jats:bold>). The investigations disclosed 6 vital factors accelerating the formation of a resting species, which plays a significant role in lowering the activities of the Mn(I) complex <jats:bold>1<\/jats:bold> in <jats:bold>ATH<\/jats:bold> and <jats:bold>AH<\/jats:bold>, respectively. In addition, we also report here a base free Mn(I) catalyzed <jats:bold>ATH<\/jats:bold> of aryl alkyl ketones with high enantioselectivity (up to 98\u2009%\u2005ee) and improved activity. More significantly, a novel and simple single\u2010step process for recycling the resting species from the catalytic leftover has been discovered. Notably, the studies provide evidence for the existence of two different temperature dependent mechanisms for <jats:bold>AH<\/jats:bold> and <jats:bold>ATH<\/jats:bold>, in contrast to previous studies on related systems.<\/jats:p>","DOI":"10.1002\/chem.202201522","type":"journal-article","created":{"date-parts":[[2022,6,2]],"date-time":"2022-06-02T08:37:39Z","timestamp":1654159059000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["Recyclable Mn(I) Catalysts for Base\u2010Free Asymmetric Hydrogenation: Mechanistic, DFT and Catalytic Studies"],"prefix":"10.1002","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4176-8510","authenticated-orcid":false,"given":"Harikrishnan","family":"Jayaprakash","sequence":"first","affiliation":[{"name":"Department of Chemistry and Applied Biosiences Swiss Federal Institute of Technology (ETH) Z\u00fcrich  8093 Z\u00fcrich 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