{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,11]],"date-time":"2026-08-11T03:33:45Z","timestamp":1786419225409,"version":"build-2736575974"},"reference-count":46,"publisher":"Wiley","issue":"49","license":[{"start":{"date-parts":[[2016,10,16]],"date-time":"2016-10-16T00:00:00Z","timestamp":1476576000000},"content-version":"am","delay-in-days":366,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#am"},{"start":{"date-parts":[[2015,10,16]],"date-time":"2015-10-16T00:00:00Z","timestamp":1444953600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"name":"DOE","award":["DE-FG02-92ER14273"],"award-info":[{"award-number":["DE-FG02-92ER14273"]}]},{"DOI":"10.13039\/100000057","name":"NIGMS","doi-asserted-by":"crossref","award":["1 P30 GM110758-01"],"award-info":[{"award-number":["1 P30 GM110758-01"]}],"id":[{"id":"10.13039\/100000057","id-type":"DOI","asserted-by":"crossref"}]},{"name":"NSF","award":["CHE-1229234"],"award-info":[{"award-number":["CHE-1229234"]}]},{"name":"NSF","award":["CRIF 1048367"],"award-info":[{"award-number":["CRIF 1048367"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2015,12]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>A chromium(I) dinitrogen complex reacts rapidly with O<jats:sub>2<\/jats:sub> to form the mononuclear dioxo complex [Tp<jats:sup><jats:italic>t<\/jats:italic>Bu,Me<\/jats:sup>Cr<jats:sup>V<\/jats:sup>(O)<jats:sub>2<\/jats:sub>] (Tp<jats:sup><jats:italic>t<\/jats:italic>Bu,Me<\/jats:sup>=hydrotris(3\u2010<jats:italic>tert<\/jats:italic>\u2010butyl\u20105\u2010methylpyrazolyl)borate), whereas the analogous reaction with sulfur stops at the persulfido complex [Tp<jats:sup><jats:italic>t<\/jats:italic>Bu,Me<\/jats:sup>Cr<jats:sup>III<\/jats:sup>(S<jats:sub>2<\/jats:sub>)]. The transformation of the putative peroxo intermediate [Tp<jats:sup><jats:italic>t<\/jats:italic>Bu,Me<\/jats:sup>Cr<jats:sup>III<\/jats:sup>(O<jats:sub>2<\/jats:sub>)] (S=<jats:sup>3<\/jats:sup>\/<jats:sub>2<\/jats:sub>) into [Tp<jats:sup><jats:italic>t<\/jats:italic>Bu,Me<\/jats:sup>Cr<jats:sup>V<\/jats:sup>(O)<jats:sub>2<\/jats:sub>] (S=<jats:sup>1<\/jats:sup>\/<jats:sub>2<\/jats:sub>) is spin\u2010forbidden. The minimum\u2010energy crossing point for the two potential energy surfaces has been identified. Although the dinuclear complex [(Tp<jats:sup><jats:italic>t<\/jats:italic>Bu,Me<\/jats:sup>Cr)<jats:sub>2<\/jats:sub>(\u03bc\u2010O)<jats:sub>2<\/jats:sub>] exists, mechanistic experiments suggest that O<jats:sub>2<\/jats:sub> activation occurs on a single metal center, by an oxidative addition on the quartet surface followed by crossover to the doublet surface.<\/jats:p>","DOI":"10.1002\/anie.201508777","type":"journal-article","created":{"date-parts":[[2015,10,16]],"date-time":"2015-10-16T13:10:20Z","timestamp":1445001020000},"page":"14974-14977","source":"Crossref","is-referenced-by-count":16,"title":["Dioxygen Activation by Non\u2010Adiabatic Oxidative Addition to a Single Metal Center"],"prefix":"10.1002","volume":"54","author":[{"given":"Eser S.","family":"Akturk","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Glenn P. A.","family":"Yap","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Klaus H.","family":"Theopold","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2015,10,16]]},"reference":[{"key":"e_1_2_3_1_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-1-4613-2475-1"},{"key":"e_1_2_3_2_2","volume-title":"Metal\u2010Catalyzed Oxidations of Organic Compounds","author":"Sheldon R. A.","year":"1981"},{"key":"e_1_2_3_3_2","unstructured":"\u00a0"},{"key":"e_1_2_3_4_2","doi-asserted-by":"publisher","DOI":"10.1007\/BFb0111572"},{"key":"e_1_2_3_5_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-1-4613-0955-0"},{"key":"e_1_2_3_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00027a001"},{"key":"e_1_2_3_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00027a002"},{"key":"e_1_2_3_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020632z"},{"key":"e_1_2_3_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020628n"},{"key":"e_1_2_3_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020633r"},{"key":"e_1_2_3_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar700043n"},{"key":"e_1_2_3_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900185x"},{"key":"e_1_2_3_13_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0535926100"},{"key":"e_1_2_3_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900269x"},{"key":"e_1_2_3_15_2","unstructured":"\u00a0"},{"key":"e_1_2_3_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar990028j"},{"key":"e_1_2_3_17_2","doi-asserted-by":"publisher","DOI":"10.1039\/b200675h"},{"key":"e_1_2_3_18_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(02)00283-7"},{"key":"e_1_2_3_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/B614390C"},{"key":"e_1_2_3_20_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0898-8838(09)00210-4"},{"key":"e_1_2_3_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/wcms.1154"},{"key":"e_1_2_3_22_2","unstructured":"\u00a0"},{"key":"e_1_2_3_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00152a015"},{"key":"e_1_2_3_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0167553"},{"key":"e_1_2_3_25_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200701933"},{"key":"e_1_2_3_25_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200701933"},{"key":"e_1_2_3_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja408357x"},{"key":"e_1_2_3_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja960157k"},{"key":"e_1_2_3_28_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5CC05993C"},{"key":"e_1_2_3_29_2","unstructured":"C48H80B2Cr2N12O2 Mr=982.86 crystal dimensions=0.339\u2005mm\u00d70.241\u2005mm\u00d70.237\u2005mm monoclinicP21\/c a=20.7125(7) b=14.7706(5) c=22.5952(8)\u2005\u00c5 \u03b2=103.7730(10)\u00b0 V=6713.9(4)\u2005\u00c53 Z=4 \u03c1calcd=0.972\u2005g\u2005cm\u22123 \u03bc=0.362\u2005mm\u22121 Mo\u2010k\u03b1:\u03bb=0.71073\u2005\u00c5 T=200(2)\u2005K 2\u03b8max=55.0 86\u2009171 reflections measured 15\u2009408 independent reflections Rint=0.0536 R1=0.0558 wR2=0.1435 residual electron density=0.802\u2005e\u2009\u00c5\u22123. Thetert\u2010butyl group on the noncoordinated pyrazole was located disordered in two positions with a refined site occupancy of 58:42. Two disordered pentane molecules of solvation per compound molecule were treated as diffused contributions. Borohydride hydrogen atoms located from difference map. CCDC\u20051414458contains the supplementary crystallographic data for this paper. These data can be obtained free of charge fromThe Cambridge Crystallographic Data Centre."},{"key":"e_1_2_3_30_2","unstructured":"A search of the Cambridge Structural Database revealed 288 complexes with terminal oxo ligands coordinated to Cr. Four of these were eliminated as outliers leaving 781 Cr\uf8feO bonds. Their mean Cr\uf8ffO distance was 1.604(31)\u2005\u00c5."},{"key":"e_1_2_3_31_2","unstructured":"C32H56BCrN6O2S2 Mr=683.75 crystal dimensions=0.438\u2005mm\u00d70.388\u2005mm\u00d70.364\u2005mm orthorhombicPnma a=18.487(14) b=21.314(16) c=9.395(7)\u2005\u00c5 V=3702(5)\u2005\u00c53 Z=4 \u03c1calcd=1.227\u2005g\u2005cm\u22123 \u03bc=0.458\u2005mm\u22121 Mo\u2010k\u03b1:\u03bb=0.71073\u2005\u00c5 T=200(2)\u2005K 2\u03b8max=56.8 48\u2009217 reflections measured 4723 independent reflections Rint=0.0418 R1=0.0405 wR2=0.1201 residual electron density=0.640\u2005e\u2009\u00c5\u22123. Compound molecule resides on a mirror plane. THF solvent molecule treated with rigid bond restraints. CCDC\u20051414459contains the supplementary crystallographic data for this paper. These data can be obtained free of charge fromThe Cambridge Crystallographic Data Centre."},{"key":"e_1_2_3_32_2","unstructured":"\u00a0"},{"key":"e_1_2_3_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00370a065"},{"key":"e_1_2_3_34_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39830001458"},{"key":"e_1_2_3_35_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(85)87212-0"},{"key":"e_1_2_3_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00148a024"},{"key":"e_1_2_3_37_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(89)85427-0"},{"key":"e_1_2_3_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00044a025"},{"key":"e_1_2_3_39_2","doi-asserted-by":"publisher","DOI":"10.1515\/znb-1993-1106"},{"key":"e_1_2_3_40_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic3020805"},{"key":"e_1_2_3_41_2","unstructured":"DFT calculations using the B3LYP functional and TZVP basis set were carried out using the program package Gaussian\u200909. Details are given in the Supportin Information. For computational economy the alkyl substituents of the Tp ligands were replaced with hydrogen atoms; the resulting compounds are labeled with a prime (\u2032)."},{"key":"e_1_2_3_42_2","doi-asserted-by":"publisher","DOI":"10.1007\/s002140050309"},{"key":"e_1_2_3_43_2","unstructured":"C24H40BCrN6O2 Mr=507.43 crystal dimensions=0.274\u2005mm\u00d70.271\u2005mm\u00d70.150\u2005mm monoclinicP21\/n a=9.309(3) b=30.574(10) c=9.374(3)\u2005\u00c5 \u03b2=101.167(6)\u00b0 V=2617.4(14)\u2005\u00c53 Z=4 \u03c1calcd=1.288\u2005g\u2005cm\u22123 \u03bc=0.467\u2005mm\u22121 Mo\u2010k\u03b1:\u03bb=0.71073\u2005\u00c5 T=100(2)\u2005K 2\u03b8max=55.0 24\u2009396 reflections measured 6001 independent reflections Rint=0.0773 R1=0.0514 wR2=0.1296 residual electron density=0.333\u2005e\u2009\u00c5\u22123. CCDC\u20051414460contains the supplementary crystallographic data for this paper. 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