{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Baek Y"],"funding":["Camille and Henry Dreyfus Foundation","Harvard University","Kwanjeong Educational Foundation","National Institute of General Medical Sciences","NIGMS NIH HHS"],"pagination":["16944-16953"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC7262787"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["141(42)"],"pubmed_abstract":["We report the catalytic C-H amination mediated by an isolable CoIII imido complex (TrL)Co(NR) supported by a sterically demanding dipyrromethene ligand (TrL = 5-mesityl-1,9-(trityl)dipyrrin). Metalation of (TrL)Li with CoCl2 in THF afforded a high-spin (S = 3/2) three-coordinate complex (TrL)CoCl. Chemical reduction of (TrL)CoCl with potassium graphite yielded the high-spin (S = 1) CoI synthon (TrL)Co which is stabilized through an intramolecular η6-arene interaction. Treatment of (TrL)Co with a stoichiometric amount of 1-azidoadamantane (AdN3) furnished a three-coordinate, diamagnetic CoIII imide (TrL)Co(NAd) as confirmed by single-crystal X-ray diffraction, revealing a rare trigonal pyramidal geometry with an acute Co-Nimido-C angle 145.0(3)°. Exposure of 1-10 mol % of (TrL)Co to linear "],"journal":["Journal of the American Chemical Society"],"pubmed_title":["Direct Manipulation of Metal Imido Geometry: Key Principles to Enhance C-H Amination Efficacy."],"pmcid":["PMC7262787"],"funding_grant_id":["GM-115815","R01 GM115815"],"pubmed_authors":["Baek Y","Hennessy ET","Betley TA"],"additional_accession":[]},"is_claimable":false,"name":"Direct Manipulation of Metal Imido Geometry: Key Principles to Enhance C-H Amination Efficacy.","description":"We report the catalytic C-H amination mediated by an isolable CoIII imido complex (TrL)Co(NR) supported by a sterically demanding dipyrromethene ligand (TrL = 5-mesityl-1,9-(trityl)dipyrrin). Metalation of (TrL)Li with CoCl2 in THF afforded a high-spin (S = 3/2) three-coordinate complex (TrL)CoCl. Chemical reduction of (TrL)CoCl with potassium graphite yielded the high-spin (S = 1) CoI synthon (TrL)Co which is stabilized through an intramolecular η6-arene interaction. Treatment of (TrL)Co with a stoichiometric amount of 1-azidoadamantane (AdN3) furnished a three-coordinate, diamagnetic CoIII imide (TrL)Co(NAd) as confirmed by single-crystal X-ray diffraction, revealing a rare trigonal pyramidal geometry with an acute Co-Nimido-C angle 145.0(3)°. Exposure of 1-10 mol % of (TrL)Co to linear ","dates":{"release":"2019-01-01T00:00:00Z","publication":"2019 Oct","modification":"2025-05-18T12:08:16.266Z","creation":"2020-06-05T07:07:21Z"},"accession":"S-EPMC7262787","cross_references":{"pubmed":["31550162"],"doi":["10.1021/jacs.9b09015"]}}