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The stability and reactivity of the MO(PP)<jats:sub>2<\/jats:sub>Cl compounds are found to depend upon the steric bulk of the phosphine ligands: derivatives with bulky phosphines that shield the oxo ligand are stable enough to be isolated, whereas those with phosphines that leave the oxo ligand exposed are more reactive and observed transiently. Magnetic measurements and DFT calculations on MoO(dppe)<jats:sub>2<\/jats:sub>Cl indicate the d<jats:sup>3<\/jats:sup> compounds are low spin with a <jats:sup>2<\/jats:sup>[(d<jats:sub><jats:italic>xy<\/jats:italic><\/jats:sub>)<jats:sup>2<\/jats:sup>(\u03c0*(MoO))<jats:sup>1<\/jats:sup>] configuration. X\u2010ray crystallographic and vibrational\u2010spectroscopic studies on d<jats:sup>2<\/jats:sup> and d<jats:sup>3<\/jats:sup> [MoO(dppe)<jats:sub>2<\/jats:sub>Cl]<jats:sup>0\/+<\/jats:sup> establish that the d<jats:sup>3<\/jats:sup> compound possesses a reduced M\u2212O bond order and significantly longer Mo\u2212O bond, accounting for its greater reactivity. These results indicate that the oxo\u2010centered reactivity of d<jats:sup>3<\/jats:sup> complexes may be controlled through ligand variation.<\/jats:p>","DOI":"10.1002\/anie.202001379","type":"journal-article","created":{"date-parts":[[2020,3,14]],"date-time":"2020-03-14T17:51:45Z","timestamp":1584208305000},"page":"10581-10586","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Synthesis, Structure, and Bonding of d<sup>3<\/sup> Molybdenum\u2013Oxo Complexes"],"prefix":"10.1002","volume":"59","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9591-7150","authenticated-orcid":false,"given":"Hunter B.","family":"Vibbert","sequence":"first","affiliation":[{"name":"Department of Chemistry The University of Chicago  Chicago IL 60637 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8378-1994","authenticated-orcid":false,"given":"Alexander S.","family":"Filatov","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Chicago  Chicago IL 60637 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0697-8152","authenticated-orcid":false,"given":"Michael D.","family":"Hopkins","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Chicago  Chicago IL 60637 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2020,4,15]]},"reference":[{"key":"e_1_2_6_1_1","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar970171h"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja037400h"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature07371"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900269x"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0cs00165a"},{"key":"e_1_2_6_7_1","unstructured":"\u00a0"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00082a005"},{"key":"e_1_2_6_9_2","doi-asserted-by":"crossref","first-page":"619","DOI":"10.1016\/B978-0-08-097774-4.00928-1","volume-title":"Comprehensive Inorganic Chemistry\u2005II, Vol.\u20059","author":"Visser S. 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