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We previously reported that a heme Fe\u2013NO model engages in this N\u2212N bond\u2010forming reaction with NO. We now demonstrate that (OEP)Co<jats:sup>II<\/jats:sup>(NO) similarly reacts with 1\u2005equiv of NO in the presence of the Lewis acids BX<jats:sub>3<\/jats:sub> (X=F, C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>) to generate N<jats:sub>2<\/jats:sub>O. DFT calculations support retention of the Co<jats:sup>II<\/jats:sup> oxidation state for the experimentally observed adduct (OEP)Co<jats:sup>II<\/jats:sup>(NO\u22c5BF<jats:sub>3<\/jats:sub>), the presumed hyponitrite intermediate (P<jats:sup>.+<\/jats:sup>)Co<jats:sup>II<\/jats:sup>(ONNO\u22c5BF<jats:sub>3<\/jats:sub>), and the porphyrin \u03c0\u2010radical cation by\u2010product of this reaction, and that the \u03c0\u2010radical cation formation likely occurs at the hyponitrite stage. In contrast, the Fe analogue undergoes a ferrous\u2010to\u2010ferric oxidation state conversion during this reaction. Our work shows that cobalt hemes are chemically competent to engage in the NO\u2010to\u2010N<jats:sub>2<\/jats:sub>O conversion reaction.<\/jats:p>","DOI":"10.1002\/anie.201909137","type":"journal-article","created":{"date-parts":[[2019,10,8]],"date-time":"2019-10-08T01:51:21Z","timestamp":1570499481000},"page":"18598-18603","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":18,"title":["Not Limited to Iron: A Cobalt Heme\u2013NO Model Facilitates N\u2013N Coupling with External NO in the Presence of a Lewis Acid to Generate N<sub>2<\/sub>O"],"prefix":"10.1002","volume":"58","author":[{"given":"Erwin G.","family":"Abucayon","sequence":"first","affiliation":[{"name":"Price Family Foundation of Structural Biology Department of Chemistry and Biochemistry University of Oklahoma  Norman OK 73019 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rahul L.","family":"Khade","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology Stevens Institute of Technology  Castle Point on Hudson Hoboken NJ 07030 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Douglas R.","family":"Powell","sequence":"additional","affiliation":[{"name":"Price Family Foundation of Structural Biology Department of Chemistry and Biochemistry University of Oklahoma  Norman OK 73019 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7207-6416","authenticated-orcid":false,"given":"Yong","family":"Zhang","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology Stevens Institute of Technology  Castle Point on Hudson Hoboken NJ 07030 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9400-0113","authenticated-orcid":false,"given":"George B.","family":"Richter\u2010Addo","sequence":"additional","affiliation":[{"name":"Price Family Foundation of Structural Biology Department of Chemistry and Biochemistry University of Oklahoma  Norman OK 73019 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2019,10,31]]},"reference":[{"key":"e_1_2_6_1_1","doi-asserted-by":"publisher","DOI":"10.1046\/j.1432-1327.1999.00186.x"},{"key":"e_1_2_6_2_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.89.12.5306"},{"key":"e_1_2_6_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/0006-291X(80)90796-2"},{"key":"e_1_2_6_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/0006-291X(81)90483-6"},{"key":"e_1_2_6_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/c39820001393"},{"key":"e_1_2_6_6_1","doi-asserted-by":"publisher","DOI":"10.1074\/jbc.274.12.7714"},{"key":"e_1_2_6_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja9603057"},{"key":"e_1_2_6_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00059a010"},{"key":"e_1_2_6_9_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0021-9258(19)45449-5"},{"key":"e_1_2_6_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja010530a"},{"key":"e_1_2_6_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200701131"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200701131"},{"key":"e_1_2_6_12_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bbabio.2012.03.001"},{"key":"e_1_2_6_13_1","doi-asserted-by":"publisher","DOI":"10.1098\/rstb.2011.0310"},{"key":"e_1_2_6_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b13681"},{"key":"e_1_2_6_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.biochem.6b00788"},{"key":"e_1_2_6_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.24396"},{"key":"e_1_2_6_17_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bbabio.2006.04.008"},{"key":"e_1_2_6_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00056a006"},{"key":"e_1_2_6_19_1","unstructured":"DFT calculations were performed using Gaussian\u200909. Full geometry optimizations were conducted using the PCM formalism with CH2Cl2solvent as used experimentally. The used method includes the mPW1PW91 functional with the basis set of Wachters\u2019 basis for cobalt 6\u2013311++G(2d 2p) for 1st shell atoms (atoms bonded to Co NO and BF3) and 6-31G(d) for other atoms. See the Supporting Information for details."},{"key":"e_1_2_6_20_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chemphys.2006.11.036"},{"key":"e_1_2_6_21_1","unstructured":"N2O yields were determined using IR spectroscopy [22]and the yields are based on the Co\/Fe reagents. In our hands the yields determined by gas chromatography were typically 5\u201310\u2009% higher than those determined by IR spectroscopy."},{"key":"e_1_2_6_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/ac60090a040"},{"key":"e_1_2_6_23_1","doi-asserted-by":"publisher","DOI":"10.2136\/sssaj2013.09.0390dgs"},{"key":"e_1_2_6_24_1","unstructured":"OEP-based \u03c0-cation radicals are known to display characteristic IR bands in the general 1520\u20131570\u2005cm\u22121range.[26]"},{"key":"e_1_2_6_25_1","unstructured":"These data are close to those of the related [(OEP\u22c5+)Co(NO)]ClO4(\u03c5NO1700\u2005cm\u22121(Nujol) \u03c51560\u2005cm\u22121).[27]The \u03c0-radical cation product [(OEP\u22c5+)Co(NO)]BF3OH (\u03c5OH\u22483525\u2005cm\u22121(KBr br)) is kinetically unstable readily converting to the neutral (OEP)Co(NO) during attempts to isolate it with a total (OEP)Co(NO) recovery of 49\u201360\u2009%."},{"key":"e_1_2_6_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00412a055"},{"key":"e_1_2_6_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00311a073"},{"key":"e_1_2_6_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic971109j"},{"key":"e_1_2_6_29_1","doi-asserted-by":"publisher","DOI":"10.1007\/s007750100274"},{"key":"e_1_2_6_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic9610748"},{"key":"e_1_2_6_31_1","unstructured":"Both [(por)CoIII]X and [(por\u22c5+)CoII]X valence isomers resulting from metal or porphyrin oxidation respectively are known but their relative stabilities depend on solvent and nature of the anion.[32\u201334]"},{"key":"e_1_2_6_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00350a017"},{"key":"e_1_2_6_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100317a020"},{"key":"e_1_2_6_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00278a047"},{"key":"e_1_2_6_35_1","unstructured":"The analogous reaction of (OEP)Fe(NO) with 2\u2005equiv of BF3\u22c5OEt2and 1\u2005equiv of NO gave N2O in approximately 16\u2009% yield (based on Fe). This same reaction using excess NO gave N2O in approximately 55\u2009% yield as reported previously.[14]"},{"key":"e_1_2_6_36_1","unstructured":"Although [K(2.2.2)]OTf by itself does not react with NO to give N2O we found that the related [K(2.2.2)]OSiMe3salt reacted with NO to give N2O in moderate yields revealing the non-innocence of some anions in these K+-salts for use in these reactions.[14]"},{"key":"e_1_2_6_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.5b00273"},{"key":"e_1_2_6_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.5b00212"},{"key":"e_1_2_6_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b11492"},{"key":"e_1_2_6_40_1","unstructured":"The free (NO)2\u2212anion has been reported to be capable of decomposing to N2O under some conditions [41 \u200942]although this is significantly enhanced in the presence of NO.[43\u201345]"},{"key":"e_1_2_6_41_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.476547"},{"key":"e_1_2_6_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp013330u"},{"key":"e_1_2_6_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp204967h"},{"key":"e_1_2_6_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp803230c"},{"key":"e_1_2_6_45_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.478967"},{"key":"e_1_2_6_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b11037"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.201909137","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201909137","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.201909137","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/am-pdf\/10.1002\/anie.201909137","content-type":"application\/pdf","content-version":"am","intended-application":"syndication"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201909137","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,9,6]],"date-time":"2023-09-06T23:46:58Z","timestamp":1694044018000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.201909137"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2019,10,31]]},"references-count":47,"journal-issue":{"issue":"51","published-print":{"date-parts":[[2019,12,16]]}},"alternative-id":["10.1002\/anie.201909137"],"URL":"https:\/\/doi.org\/10.1002\/anie.201909137","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2019,10,31]]},"assertion":[{"value":"2019-07-22","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2019-10-31","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}