{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,23]],"date-time":"2026-04-23T21:57:03Z","timestamp":1776981423231,"version":"3.51.4"},"reference-count":52,"publisher":"Wiley","issue":"36","license":[{"start":{"date-parts":[[2020,7,4]],"date-time":"2020-07-04T00:00:00Z","timestamp":1593820800000},"content-version":"am","delay-in-days":332,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#am"},{"start":{"date-parts":[[2019,8,7]],"date-time":"2019-08-07T00:00:00Z","timestamp":1565136000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100006770","name":"American Chemical Society Petroleum Research Fund","doi-asserted-by":"publisher","award":["55989-DNI3"],"award-info":[{"award-number":["55989-DNI3"]}],"id":[{"id":"10.13039\/100006770","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["1650894"],"award-info":[{"award-number":["1650894"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2019,9,2]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Bond distance is a common structural metric used to assess changes in metal\u2013ligand bonds, but it is not clear how sensitive changes in bond distances are with respect to changes in metal\u2013ligand covalency. Here we report ligand K\u2010edge XAS studies on Ni and Pd complexes containing different phosphorus(III) ligands. Despite the large number of electronic and structural permutations, P K\u2010edge pre\u2010edge peak intensities reveal a remarkable correlation that spectroscopically quantifies the linear interdependence of covalent M\u2212P \u03c3 bonding and bond distance. Cl K\u2010edge studies conducted on many of the same Ni and Pd compounds revealed a poor correlation between M\u2212Cl bond distance and covalency, but a strong correlation was established by analyzing Cl K\u2010edge data for Ti complexes with a wider range of Ti\u2212Cl bond distances. Together these results establish a quantitative framework to begin making more accurate assessments of metal\u2013ligand covalency using bond distances from readily\u2010available crystallographic data.<\/jats:p>","DOI":"10.1002\/anie.201905635","type":"journal-article","created":{"date-parts":[[2019,7,4]],"date-time":"2019-07-04T17:45:54Z","timestamp":1562262354000},"page":"12451-12455","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":23,"title":["Quantifying the Interdependence of Metal\u2013Ligand Covalency and Bond Distance Using Ligand K\u2010edge XAS"],"prefix":"10.1002","volume":"58","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3836-127X","authenticated-orcid":false,"given":"Kyounghoon","family":"Lee","sequence":"first","affiliation":[{"name":"Department of Chemistry The University of Iowa  E331 Chemistry Building Iowa City IA 52242-1294 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Anastasia V.","family":"Blake","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Iowa  E331 Chemistry Building Iowa City IA 52242-1294 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Courtney M.","family":"Donahue","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Iowa  E331 Chemistry Building Iowa City IA 52242-1294 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kyle D.","family":"Spielvogel","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Iowa  E331 Chemistry Building Iowa City IA 52242-1294 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Brian J.","family":"Bellott","sequence":"additional","affiliation":[{"name":"Department of Chemistry Western Illinois University  1 University Circle Macomb IL 61455 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6229-0822","authenticated-orcid":false,"given":"Scott R.","family":"Daly","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Iowa  E331 Chemistry Building Iowa City IA 52242-1294 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2019,8,7]]},"reference":[{"key":"e_1_2_2_1_1","volume-title":"The nature of the chemical bond and the structure of molecules and crystals: an introduction to modern structural chemistry","author":"Pauling L.","year":"1960"},{"key":"e_1_2_2_2_1","unstructured":"\u00a0"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1007\/b136230"},{"key":"e_1_2_2_4_2","volume-title":"Metal-ligand multiple bonds: the chemistry of transition metal complexes containing oxo, nitrido, imido, alkylidene, or alkylidyne ligands","author":"Nugent W. A.","year":"1988"},{"key":"e_1_2_2_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2012.04.029"},{"key":"e_1_2_2_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar50152a005"},{"key":"e_1_2_2_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201101447"},{"key":"e_1_2_2_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic034198a"},{"key":"e_1_2_2_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/B411434E"},{"key":"e_1_2_2_10_1","unstructured":"\u00a0"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar990125c"},{"key":"e_1_2_2_12_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2004.03.020"},{"key":"e_1_2_2_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6b02875"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2012.07.020"},{"key":"e_1_2_2_15_2","doi-asserted-by":"publisher","DOI":"10.1080\/02603594.2018.1465938"},{"key":"e_1_2_2_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp5086763"},{"key":"e_1_2_2_17_1","unstructured":"\u00a0"},{"key":"e_1_2_2_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja2105015"},{"key":"e_1_2_2_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja310223b"},{"key":"e_1_2_2_20_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4DT02302A"},{"key":"e_1_2_2_21_1","unstructured":"\u00a0"},{"key":"e_1_2_2_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic503125b"},{"key":"e_1_2_2_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201800203"},{"key":"e_1_2_2_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp5086763"},{"key":"e_1_2_2_25_1","unstructured":"\u00a0"},{"key":"e_1_2_2_26_2","doi-asserted-by":"publisher","DOI":"10.1039\/C7DT02144E"},{"key":"e_1_2_2_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.8b01601"},{"key":"e_1_2_2_28_2","doi-asserted-by":"publisher","DOI":"10.1039\/b104122n"},{"key":"e_1_2_2_29_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1099-0682(199802)1998:2<155::AID-EJIC155>3.0.CO;2-T"},{"key":"e_1_2_2_30_1","doi-asserted-by":"publisher","DOI":"10.1039\/b801115j"},{"key":"e_1_2_2_31_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0567739476001551"},{"key":"e_1_2_2_32_1","unstructured":"Ionic radii for P in our PIIIligands are not included in common tabulated values so we used the extrapolated values of 2.42 and 2.55\u2005\u00c5 from the linear regressions as the sum of ionic radii. This allowed the ionic radii of P to be calculated by subtracting the tabulated radii for Ni2+and Pd2+to yield 1.93\u00b10.11 and 1.91\u00b10.27\u2005\u00c5 respectively (for comparison the ionic radius reported for chloride is 1.81\u2005\u00c5; see Ref.\u2005[15])."},{"key":"e_1_2_2_33_1","unstructured":"\u00a0"},{"key":"e_1_2_2_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja7108486"},{"key":"e_1_2_2_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja076537v"},{"key":"e_1_2_2_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja809834k"},{"key":"e_1_2_2_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja302660k"},{"key":"e_1_2_2_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic202453c"},{"key":"e_1_2_2_39_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jlumin.2015.05.011"},{"key":"e_1_2_2_40_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6DT00200E"},{"key":"e_1_2_2_41_1","unstructured":"\u00a0"},{"key":"e_1_2_2_42_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00097a009"},{"key":"e_1_2_2_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00113a015"},{"key":"e_1_2_2_44_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2007.07.032"},{"key":"e_1_2_2_45_1","unstructured":"\u00a0"},{"key":"e_1_2_2_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja044827v"},{"key":"e_1_2_2_47_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic060402t"},{"key":"e_1_2_2_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic8004932"},{"key":"e_1_2_2_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9015759"},{"key":"e_1_2_2_50_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.8b01511"},{"key":"e_1_2_2_51_1","unstructured":"Qualitative correlations between Ti\u2212Cl bond distance and Cl K-edge pre-edge intensities were noted previously for subsets of the data included in Figure\u20054. See Refs.\u2005[19a b]."},{"key":"e_1_2_2_52_1","unstructured":"It is important to note that Cl K-edge data collected on the Ti complexes quantifies both \u03c3 and \u03c0 contributions to covalent M\u2212Cl bonds whereas those for the Ni and Pd complexes only capture covalent M\u2212Cl \u03c3 bonding (as shown in Figure\u20051). The influence this difference may have on metal-ligand bond distance\/covalency correlations remains an open question."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.201905635","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201905635","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.201905635","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/am-pdf\/10.1002\/anie.201905635","content-type":"application\/pdf","content-version":"am","intended-application":"syndication"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201905635","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,9,8]],"date-time":"2023-09-08T13:34:49Z","timestamp":1694180089000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.201905635"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2019,8,7]]},"references-count":52,"journal-issue":{"issue":"36","published-print":{"date-parts":[[2019,9,2]]}},"alternative-id":["10.1002\/anie.201905635"],"URL":"https:\/\/doi.org\/10.1002\/anie.201905635","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2019,8,7]]},"assertion":[{"value":"2019-05-06","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2019-08-07","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}