{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,1]],"date-time":"2026-09-01T13:14:30Z","timestamp":1788268470381,"version":"build-2803163510"},"reference-count":46,"publisher":"American Chemical Society (ACS)","issue":"50","license":[{"start":{"date-parts":[[2017,11,28]],"date-time":"2017-11-28T00:00:00Z","timestamp":1511827200000},"content-version":"vor","delay-in-days":365,"URL":"https:\/\/pubs.acs.org\/page\/policy\/authorchoice_termsofuse.html"}],"funder":[{"DOI":"10.13039\/100000165","name":"Division of Chemistry","doi-asserted-by":"publisher","award":["CHE-1362118"],"award-info":[{"award-number":["CHE-1362118"]}],"id":[{"id":"10.13039\/100000165","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000038","name":"Natural Sciences and Engineering Research Council of Canada","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/501100000038","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2016,12,21]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Toward the preparation of a coordination complex of the heterodiatomic molecule PN, P\u2261N-V(N[tBu]Ar)3 (1, Ar = 3,5-Me2C6H3), we report the use of ClPA (A = C14H10, anthracene) as a formal source of phosphorus(I) in its reaction with Na[NV(N[tBu]Ar)3] (Na[4]) to yield trimeric cyclo-triphosphane [PNV(N[tBu]Ar)3]3 (3) with a core composed exclusively of phosphorus and nitrogen. In the presence of NapS2 (peri-1,8-naphthalene disulfide), NapS2P-NV(N[tBu]Ar)3 (6) is instead generated in 80% yield, suggesting trapping of transient 1. Upon mild heating, 3 readily fragments into dimeric [PNV(N[tBu]Ar)3]2 (2), while in the presence of bis(trimethylsilyl)acetylene or cis-4-octene, the respective phosphirene (Ar[tBu]N)3VN-PC2(SiMe3)2 (7) or phosphirane (Ar[tBu]N)3VN-P(C8H16) (8) compounds are generated. Kinetic data were found to be consistent with unimolecular decay of 3, and [2+1]-cycloaddition with radical clocks ruled out a triplet intermediate, consistent with intermediate 1 reacting as a singlet phosphinidene. In addition, both 7 and 8 were shown to reversibly exchange cis-4-octene and bis(trimethylsilyl)acetylene, serving as formal sources of 1, a reactivity manifold traditionally reserved for transition metals.<\/jats:p>","DOI":"10.1021\/jacs.6b10545","type":"journal-article","created":{"date-parts":[[2016,11,28]],"date-time":"2016-11-28T11:34:40Z","timestamp":1480332880000},"page":"16220-16223","source":"Crossref","is-referenced-by-count":45,"title":["Phosphinidene\nReactivity of a Transient Vanadium P\u2261N\nComplex"],"prefix":"10.1021","volume":"138","author":[{"given":"Marc-Andre\u0301","family":"Courtemanche","sequence":"first","affiliation":[{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"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":[[2016,11,28]]},"reference":[{"key":"2026090108215122900_cit1","doi-asserted-by":"publisher","first-page":"1061","DOI":"10.1002\/adsc.200303081","volume":"345","author":"Shaver","year":"2003","journal-title":"Adv. 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