Halbach, Robert L.Gygi, DavidBloch, Eric D.Anderson, Bryce L.Nocera, Daniel2018-07-252018Halbach, Robert L., David Gygi, Eric D. Bloch, Bryce L. Anderson, and Daniel G. Nocera. 2018. “Structurally characterized terminal manganese(iv) oxo tris(alkoxide) complex† †Electronic supplementary information (ESI) available: Single crystal X-ray diffraction data; ESI-MS spectra and data: IR spectra; and magnetic data. CCDC 1829119–1829121. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc01164h.” Chemical Science 9 (19): 4524-4528. doi:10.1039/c8sc01164h. http://dx.doi.org/10.1039/c8sc01164h.http://nrs.harvard.edu/urn-3:HUL.InstRepos:37298567A Mn(iv) complex featuring a terminal oxo ligand, [MnIV(O)(ditox)3][K(15-C-5)2] (3; ditox = tBu2MeCO–, 15-C-5 = 15-crown-5-ether) has been isolated and structurally characterized. Treatment of the colorless precursor [MnII(ditox)3][K(15-C-5)2] (2) with iodosobenzene affords 3 as a green free-flowing powder in high yields. The X-ray crystal structure of 3 reveals a pseudotetrahedral geometry about the central Mn, which features a terminal oxo (d(Mn–Oterm = 1.628(2) Å)). EPR spectroscopy, SQUID magnetometry, and Evans method magnetic susceptibility indicate that 3 consists of a high-spin S = 3/2 Mn(iv) metal center. 3 promotes C–H bond activation by a hydrogen atom abstraction. The [MnIV(O)(ditox)3]– furnishes a model for the proposed terminal oxo of the unique manganese of the oxygen evolving complex of photosystem II.en-USJournal Article2018-07-2510.1039/c8sc01164h