{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,2]],"date-time":"2026-09-02T04:14:48Z","timestamp":1788322488260,"version":"build-2803163510"},"reference-count":46,"publisher":"American Chemical Society (ACS)","issue":"34","license":[{"start":{"date-parts":[[2019,8,20]],"date-time":"2019-08-20T00:00:00Z","timestamp":1566259200000},"content-version":"vor","delay-in-days":7,"URL":"https:\/\/pubs.acs.org\/page\/policy\/authorchoice_ccbyncnd_termsofuse.html"}],"funder":[{"DOI":"10.13039\/100000165","name":"Division of Chemistry","doi-asserted-by":"publisher","award":["1664799"],"award-info":[{"award-number":["1664799"]}],"id":[{"id":"10.13039\/100000165","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2019,8,28]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Catalytic phosphiranation has been achieved, allowing preparation of trans-1-R-2-phenylphosphiranes (R = t-Bu: 1-t-Bu; i-Pr: 1-i-Pr) from the corresponding dibenzo-7-(R)-7-phospha-norbornadiene (RPA, A = C14H10, anthracene) and styrene in 73% and 57% isolated yields, respectively. The cocatalyst system requires tetramethylammonium fluoride (TMAF) and [Fp(THF)][BF4] (Fp = Fe(\u03b75-C5H5)(CO)2). In the case of the t-Bu derivative, the reaction mechanism was probed using stoichiometric reaction studies, a Hammett analysis, and a deuterium labeling experiment. Together, these suggest the intermediacy of iron-phosphido FpP(F)(t-Bu) (2), generated independently from the stoichiometric reaction of [Fp(t-BuPA)][BF4] with TMAF. Two other plausible reaction intermediates, [Fp(t-BuPA)][BF4] and [Fp(1-t-Bu)][BF4], were prepared independently and structurally characterized.<\/jats:p>","DOI":"10.1021\/jacs.9b07069","type":"journal-article","created":{"date-parts":[[2019,8,13]],"date-time":"2019-08-13T18:39:30Z","timestamp":1565721570000},"page":"13336-13340","source":"Crossref","is-referenced-by-count":33,"title":["Organoiron-\nand Fluoride-Catalyzed Phosphinidene Transfer\nto Styrenic Olefins in a Stereoselective Synthesis of Unprotected\nPhosphiranes"],"prefix":"10.1021","volume":"141","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9228-7947","authenticated-orcid":true,"given":"Michael B.","family":"Geeson","sequence":"first","affiliation":[{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7445-5663","authenticated-orcid":true,"given":"Wesley J.","family":"Transue","sequence":"additional","affiliation":[{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2568-3269","authenticated-orcid":true,"given":"Christopher C.","family":"Cummins","sequence":"additional","affiliation":[{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2019,8,13]]},"reference":[{"key":"2026090123281312300_cit1a","doi-asserted-by":"publisher","first-page":"977","DOI":"10.1021\/cr010007e","article-title":"Stereoselective\nCyclopropanation Reactions","volume":"103","author":"Lebel","year":"2003","journal-title":"Chem. 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Elem."},{"key":"2026090123281312300_cit2d","doi-asserted-by":"publisher","first-page":"2478","DOI":"10.1002\/1521-3773(20000717)39:14&lt;2478::AID-ANIE2478&gt;3.0.CO;2-G","article-title":"BABAR-Phos\nRhodium Complexes: Reversible Metal Insertion into a Three-Membered\nRing and Catalytic Hydroborations","volume":"39","author":"Liedtke","year":"2000","journal-title":"Angew. Chem.,\nInt. Ed."},{"key":"2026090123281312300_cit3a","doi-asserted-by":"publisher","first-page":"567","DOI":"10.1002\/marc.1994.030150618","article-title":"Ring-opening polymerization\nof 1-(2,4,6-tri-tert-butylphenyl)-phosphirane:\ndirect synthesis of a polyphosphine derivative","volume":"15","author":"Kobayashi","year":"1994","journal-title":"Macromol. Rapid Commun."},{"key":"2026090123281312300_cit3b","doi-asserted-by":"publisher","first-page":"1387","DOI":"10.1080\/10426500212283","article-title":"New Ring-Opening Polymerization of Phosphorus-Containing\nCyclic Monomers","volume":"177","author":"Kadokawa","year":"2002","journal-title":"Phosphorus, Sulfur Silicon\nRelat. Elem."},{"key":"2026090123281312300_cit4","doi-asserted-by":"publisher","first-page":"1170","DOI":"10.1021\/acs.organomet.6b00227","article-title":"iPr2N\u2013P=Fe(CO)4 in Olefinic Solvents: A Reservoir of a Transient Phosphinidene\nComplex Capable of Substrate Hopping","volume":"35","author":"Wit","year":"2016","journal-title":"Organometallics"},{"key":"2026090123281312300_cit5","doi-asserted-by":"publisher","first-page":"456","DOI":"10.1021\/om00081a021","article-title":"The carbene-like behavior\nof terminal phosphinidene\ncomplexes toward olefins. 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Chem."},{"key":"2026090123281312300_cit25","doi-asserted-by":"publisher","first-page":"4285","DOI":"10.1002\/cber.19851181036","article-title":"Beitra\u0308ge\nzur Chemie des Phosphors, 154. 1-tert-Butyl-2-methylphosphiran\n\u2013 ein thermisch besta\u0308ndiges\nMonophosphiran","volume":"118","author":"Baudler","year":"1985","journal-title":"Chem. Ber."},{"key":"2026090123281312300_cit26","doi-asserted-by":"publisher","first-page":"8274","DOI":"10.1039\/c1cc12440d","article-title":"Taming\nfunctionality: easy-to-handle\nchiral phosphiranes","volume":"47","author":"Ficks","year":"2011","journal-title":"Chem. Commun."},{"key":"2026090123281312300_cit27a","doi-asserted-by":"publisher","first-page":"12343","DOI":"10.1021\/ic301652u","article-title":"Synthesis and Reactions of the First\nRoom Temperature Stable Li\/Cl Phosphinidenoid Complex","volume":"51","author":"Nesterov","year":"2012","journal-title":"Inorg. 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Educ."},{"key":"2026090123281312300_cit30","doi-asserted-by":"publisher","first-page":"4365","DOI":"10.1021\/om00060a069","article-title":"Hammett reaction\nconstant for a terminal methylphosphinidene\ncomplex","volume":"11","author":"Hung","year":"1992","journal-title":"Organometallics"},{"key":"2026090123281312300_cit31","doi-asserted-by":"publisher","first-page":"1323","DOI":"10.1021\/om00149a031","article-title":"Cycloaddition of\nalkenes and alkynes to CpFe(CO)2PR2 to give\nCp(CO)FePR2C=CC=O heterometallacycles","volume":"6","author":"Ashby","year":"1987","journal-title":"Organometallics"},{"key":"2026090123281312300_cit32","doi-asserted-by":"publisher","first-page":"807","DOI":"10.1002\/open.201900176","article-title":"Acylation Reactions of Dibenzo-7-phosphanorbornadiene:\nDFT Mechanistic Insights","volume":"8","author":"Qu","year":"2019","journal-title":"ChemistryOpen"},{"key":"2026090123281312300_cit33","doi-asserted-by":"publisher","first-page":"1526","DOI":"10.1021\/om960400o","article-title":"Synthesis\nand Reactivity of Phosphirane\nLigands and the Structural Characterization of Cp*IrCl2(tert-butylphosphirane)","volume":"16","author":"Me\u0301zailles","year":"1997","journal-title":"Organometallics"},{"key":"2026090123281312300_cit34","doi-asserted-by":"publisher","first-page":"9507","DOI":"10.1002\/anie.201703590","article-title":"Polymerization of\n1-Phosphaisoprene: Synthesis and Characterization of a Chemically\nFunctional Phosphorus Version of Natural Rubber","volume":"56","author":"Du\u0308ck","year":"2017","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090123281312300_cit35","doi-asserted-by":"publisher","first-page":"922","DOI":"10.1039\/C5CS00725A","article-title":"Polymers and the\np-block elements","volume":"45","author":"Priegert","year":"2016","journal-title":"Chem. Soc. 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