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While the variation of phosphine and NHC moieties led to inferior results than for a parent system, the incorporation of a phenyl substituent into the ligand methylene bridge improved catalytic performance by <jats:italic>ca<\/jats:italic>. 3 times providing maximal TON values in the range of 15000\u201320000. Mechanistic investigation combining experimental and computational studies allowed to rationalize this beneficial effect as an enhanced stabilization of reaction intermediates including anionic hydride species <jats:italic>fac<\/jats:italic>\u2010[(Ph<jats:sub>2<\/jats:sub>PC(Ph)NHC)Mn(CO)<jats:sub>3<\/jats:sub>H]<jats:sup>\u2212<\/jats:sup> playing a crucial role in the hydrogenation process. 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