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Catalytic nitrogen reduction (N\n                    <jats:sub>2<\/jats:sub>\n                    R) provides a salient example; whereas ammonia (NH\n                    <jats:sub>3<\/jats:sub>\n                    ) is the common product of N\n                    <jats:sub>2<\/jats:sub>\n                    R, hydrazine (N\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    ) is produced under certain conditions. Using mechanism\u2010guided design, we report a strategy for tuning redox potential that enables selective reduction of dinitrogen to hydrazine by iron complexes in polar protic media. Incorporation of cationic trimethylammonium (NMe\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>+<\/jats:sup>\n                    ) or proton\u2010responsive dimethylamino (NMe\n                    <jats:sub>2<\/jats:sub>\n                    ) groups into a tris(phosphino)borane (P\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>B<\/jats:sup>\n                    ) ligand framework affords redox\u2010tunable iron precatalysts that operate efficiently in methanol. Computational analyses reveal that these ligand modifications anodically shift the reduction potential of an iron hydrazido (Fe\u2550NNH\n                    <jats:sub>2<\/jats:sub>\n                    ) intermediate by &gt;400\u00a0mV, thereby influencing the key branch point for hydrazine versus ammonia. Critical to success is positioning the cationic charges remote from the Fe\u2013N\n                    <jats:sub>2<\/jats:sub>\n                    binding site to preserve the high degree of N\n                    <jats:sub>2<\/jats:sub>\n                    activation required for functionalization. Newly prepared tricationic iron complexes, soluble and stable in polar protic media, catalyze N\n                    <jats:sub>2<\/jats:sub>\n                    R with N\u2010fixed yields of up to 73% per reducing equivalent consumed, and with hydrazine selectivity exceeding 20:1 over ammonia. This work highlights the use of remote electrostatic effects to tune multi\u2010electron catalytic product profiles from a 6e\n                    <jats:sup>\u2013<\/jats:sup>\n                    to a 4e\n                    <jats:sup>\u2013<\/jats:sup>\n                    product.\n                  <\/jats:p>","DOI":"10.1002\/anie.202524836","type":"journal-article","created":{"date-parts":[[2026,2,10]],"date-time":"2026-02-10T04:59:37Z","timestamp":1770699577000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Remote Positioning of Cations Tunes Catalytic Fe\u2010Mediated Nitrogen Fixation Selectivity for Hydrazine Instead of Ammonia in Protic Media"],"prefix":"10.1002","volume":"65","author":[{"given":"Lucie","family":"Nurdin","sequence":"first","affiliation":[{"name":"Division of Chemistry and Chemical Engineering California Institute of Technology (Caltech)  Pasadena California USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hoimin","family":"Jung","sequence":"additional","affiliation":[{"name":"Division of Chemistry and Chemical Engineering California Institute of Technology (Caltech)  Pasadena California USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6610-4414","authenticated-orcid":false,"given":"Jonas C.","family":"Peters","sequence":"additional","affiliation":[{"name":"Division of Chemistry and Chemical Engineering California Institute of Technology (Caltech)  Pasadena California 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