{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,20]],"date-time":"2026-09-20T12:47:22Z","timestamp":1789908442324,"version":"4.0.1"},"reference-count":41,"publisher":"American Chemical Society (ACS)","issue":"12","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J. Am. Chem. Soc."],"published-print":{"date-parts":[[2009,4,1]]},"DOI":"10.1021\/ja9005699","type":"journal-article","created":{"date-parts":[[2009,3,9]],"date-time":"2009-03-09T12:24:06Z","timestamp":1236601446000},"page":"4236-4238","source":"Crossref","is-referenced-by-count":54,"title":["Fluxionality of [(Ph<sub>3<\/sub>P)<sub>3<\/sub>Rh(X)]: The Extreme Case of X = CF<sub>3<\/sub>"],"prefix":"10.1021","volume":"131","author":[{"given":"Jenni","family":"Goodman","sequence":"first","affiliation":[{"name":"Central Research & Development, E. I. DuPont de Nemours & Co., Inc., Experimental Station, Wilmington, Delaware 19880, and School of Engineering and Physical Sciences, William H. Perkin Building, Heriot-Watt University, Edinburgh EH14 4AS, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Vladimir V.","family":"Grushin","sequence":"additional","affiliation":[{"name":"Central Research & Development, E. I. DuPont de Nemours & Co., Inc., Experimental Station, Wilmington, Delaware 19880, and School of Engineering and Physical Sciences, William H. Perkin Building, Heriot-Watt University, Edinburgh EH14 4AS, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Roman B.","family":"Larichev","sequence":"additional","affiliation":[{"name":"Central Research & Development, E. I. DuPont de Nemours & Co., Inc., Experimental Station, Wilmington, Delaware 19880, and School of Engineering and Physical Sciences, William H. Perkin Building, Heriot-Watt University, Edinburgh EH14 4AS, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Stuart A.","family":"Macgregor","sequence":"additional","affiliation":[{"name":"Central Research & Development, E. I. DuPont de Nemours & Co., Inc., Experimental Station, Wilmington, Delaware 19880, and School of Engineering and Physical Sciences, William H. Perkin Building, Heriot-Watt University, Edinburgh EH14 4AS, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"William J.","family":"Marshall","sequence":"additional","affiliation":[{"name":"Central Research & Development, E. I. DuPont de Nemours & Co., Inc., Experimental Station, Wilmington, Delaware 19880, and School of Engineering and Physical Sciences, William H. Perkin Building, Heriot-Watt University, Edinburgh EH14 4AS, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"D. Christopher","family":"Roe","sequence":"additional","affiliation":[{"name":"Central Research & Development, E. I. DuPont de Nemours & Co., Inc., Experimental Station, Wilmington, Delaware 19880, and School of Engineering and Physical Sciences, William H. Perkin Building, Heriot-Watt University, Edinburgh EH14 4AS, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2009,3,9]]},"reference":[{"key":"ref1\/cit1","doi-asserted-by":"crossref","first-page":"63","DOI":"10.1002\/9780470166291.ch2","volume":"28","author":"Jardine F. H.","year":"1981","journal-title":"Prog. Inorg. Chem."},{"key":"ref2\/cit2a","doi-asserted-by":"crossref","first-page":"P25","DOI":"10.1016\/S0022-328X(00)83654-2","volume":"8","author":"Keim W.","year":"1967","journal-title":"J. Organomet. Chem."},{"key":"ref2\/cit2b","doi-asserted-by":"crossref","first-page":"179","DOI":"10.1016\/S0022-328X(00)92654-8","volume":"14","author":"Keim W.","year":"1968","journal-title":"J. Organomet. Chem."},{"key":"ref3\/cit3","doi-asserted-by":"crossref","first-page":"546","DOI":"10.1021\/ic50061a033","volume":"7","author":"Dewhirst K. C.","year":"1968","journal-title":"Inorg. Chem."},{"key":"ref4\/cit4","doi-asserted-by":"crossref","first-page":"3064","DOI":"10.1021\/ic50189a019","volume":"17","author":"Strauss S. H.","year":"1978","journal-title":"Inorg. Chem."},{"key":"ref5\/cit5","doi-asserted-by":"crossref","first-page":"407","DOI":"10.1016\/0022-328X(89)85150-2","volume":"376","author":"Price R. T.","year":"1989","journal-title":"J. Organomet. Chem."},{"key":"ref6\/cit6a","doi-asserted-by":"crossref","first-page":"3068","DOI":"10.1021\/ja049844z","volume":"126","author":"Grushin V. V.","year":"2004","journal-title":"J. Am. Chem. Soc."},{"key":"ref6\/cit6b","doi-asserted-by":"crossref","first-page":"15304","DOI":"10.1021\/ja054506z","volume":"127","author":"Macgregor S. A.","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"ref7\/cit7","doi-asserted-by":"crossref","first-page":"1293","DOI":"10.1021\/cr00089a014","volume":"88","author":"Brothers J. P.","year":"1988","journal-title":"Chem. Rev."},{"key":"ref8\/cit8a","doi-asserted-by":"crossref","first-page":"8916","DOI":"10.1021\/ja001646u","volume":"122","author":"Huang D.","year":"2000","journal-title":"J. Am. Chem. Soc."},{"key":"ref8\/cit8b","doi-asserted-by":"crossref","first-page":"3185","DOI":"10.1021\/ja963903u","volume":"119","author":"Huang D.","year":"1997","journal-title":"J. Am. Chem. Soc."},{"key":"ref9\/cit9a","doi-asserted-by":"crossref","first-page":"391","DOI":"10.1016\/0022-328X(90)85384-B","volume":"388","author":"Burrell A. K.","year":"1990","journal-title":"J. Organomet. Chem."},{"key":"ref10\/cit10","unstructured":"See theSupporting Informationfor details."},{"key":"ref11\/cit11","unstructured":"NMR data for2(C6D6, 20\u2009\u00b0C, \u03b4):19F: \u22122.4 (dq,JF\u2212P= 32 Hz,JF\u2212Rh= 11.5 Hz).31P: 29.4 (dq,JP\u2212F= 32 Hz,JP\u2212Rh= 158 Hz)."},{"key":"ref12\/cit12","unstructured":"Second-order31P NMR spectra have been previously observed for similar Rh(I) \u03c3-aryls [(Me3P)3Rh(Ar)] (Ar = Ph, Tol).(5)"},{"key":"ref13\/cit13","volume-title":"Gaussian 03","author":"Frisch M. J.","year":"2001"},{"key":"ref14\/cit14","unstructured":"Triplet [(H3P)3Rh(Cl)] (E= +22.7 kcal mol\u22121) is more stable than the singlet TS. This represents the lower limit for the barrier to phosphine exchange via a spin-crossover mechanism but is still too high to be accessed at room temperature. Triplet [(H3P)3Rh(CF3)] (E= +27.4 kcal mol\u22121) is much higher in energy than singletTS(2\u2032-I\u2032)andI\u2032."},{"key":"ref15\/cit15","doi-asserted-by":"crossref","first-page":"273","DOI":"10.1023\/A:1020209324950","volume":"32","author":"Fernandes M. A.","year":"2002","journal-title":"J. Chem. Crystallogr."},{"key":"ref16\/cit16","unstructured":"Relating \u0394Hcalc\u29e7to fluxionality rates assumes similar entropic changes for all X. Entropy changes are difficult to address accurately in the present calculations because of the absence of solvent effects. Generally, \u0394Scalc\u29e7was a small positive value, possibly because of the greater space available to the PPh3ligands in the TS. One exception, however, was [(Ph3P)3Rh(H)], where a small negative value of \u0394Scalc\u29e7was computed.(10)"},{"key":"ref17\/cit17","doi-asserted-by":"crossref","first-page":"1143","DOI":"10.1021\/om0610703","volume":"26","author":"Macgregor S. A.","year":"2007","journal-title":"Organometallics"},{"key":"ref18\/cit18","doi-asserted-by":"crossref","first-page":"335","DOI":"10.1016\/S0010-8545(00)80238-6","volume":"10","author":"Appleton T. G.","year":"1973","journal-title":"Coord. Chem. Rev."},{"key":"ref19\/cit19a","doi-asserted-by":"crossref","first-page":"183","DOI":"10.1016\/S0065-3055(08)60511-0","volume":"31","author":"Hughes R. P.","year":"1990","journal-title":"Adv. Organomet. Chem."},{"key":"ref19\/cit19b","doi-asserted-by":"crossref","first-page":"211","DOI":"10.1016\/S0065-3055(08)60492-X","volume":"35","author":"Morrison J. A.","year":"1993","journal-title":"Adv. Organomet. Chem."},{"key":"ref20\/cit20","volume-title":"Orbital Interactions in Chemistry","author":"Albright T. A.","year":"1985"},{"key":"ref21\/cit21a","doi-asserted-by":"crossref","first-page":"1061","DOI":"10.1021\/ic50194a036","volume":"18","author":"Bennett M. A.","year":"1979","journal-title":"Inorg. Chem."},{"key":"ref21\/cit21b","doi-asserted-by":"crossref","first-page":"1071","DOI":"10.1021\/ic50194a037","volume":"18","author":"Bennett M. A.","year":"1979","journal-title":"Inorg. Chem."},{"key":"ref21\/cit21c","doi-asserted-by":"crossref","first-page":"747","DOI":"10.1021\/ic030251j","volume":"43","author":"Hughes R. P.","year":"2004","journal-title":"Inorg. Chem."},{"key":"ref21\/cit21d","doi-asserted-by":"crossref","first-page":"4632","DOI":"10.1021\/ja0602389","volume":"128","author":"Grushin V. V.","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref22\/cit22","doi-asserted-by":"crossref","first-page":"1842","DOI":"10.1021\/ja9710114","volume":"120","author":"Landis C. R.","year":"1998","journal-title":"J. Am. Chem. Soc."},{"key":"ref23\/cit23a","doi-asserted-by":"crossref","DOI":"10.1002\/9780470988589","volume-title":"Organofluorine Chemistry","author":"Uneyama K.","year":"2006"},{"key":"ref24\/cit24a","doi-asserted-by":"crossref","first-page":"4253","DOI":"10.1021\/ja00993a001","volume":"89","author":"Pople J. A.","year":"1967","journal-title":"J. Am. Chem. Soc."},{"key":"ref24\/cit24b","doi-asserted-by":"crossref","first-page":"237","DOI":"10.1063\/1.1680774","volume":"60","author":"Davis D. W.","year":"1974","journal-title":"J. Chem. Phys."},{"key":"ref24\/cit24c","doi-asserted-by":"crossref","first-page":"2337","DOI":"10.1021\/ja00842a004","volume":"97","author":"Holmes S. A.","year":"1975","journal-title":"J. Am. Chem. Soc."},{"key":"ref25\/cit25a","unstructured":"aNotably, the overall charge on the CF3ligand (\u22120.30) is roughly the same as on the CH3group (\u22120.29; Figure3). Hence, the CF3ligand should not be viewed as carbocationic.(25b, 25c)"},{"key":"ref25\/cit25b","doi-asserted-by":"crossref","first-page":"3132","DOI":"10.1021\/ic990572o","volume":"38","author":"Christe K. O.","year":"1999","journal-title":"Inorg. Chem."},{"key":"ref25\/cit25c","doi-asserted-by":"crossref","first-page":"481","DOI":"10.1021\/ja9933137","volume":"122","author":"Christe K. O.","year":"2000","journal-title":"J. Am. Chem. Soc."},{"key":"ref26\/cit26a","doi-asserted-by":"crossref","first-page":"172","DOI":"10.1016\/S0020-1693(98)00171-6","volume":"280","author":"Kuznetsov V. F.","year":"1998","journal-title":"Inorg. Chim. Acta"},{"key":"ref26\/cit26b","doi-asserted-by":"crossref","first-page":"3007","DOI":"10.1016\/j.ica.2004.02.030","volume":"357","author":"Osakada K.","year":"2004","journal-title":"Inorg. Chim. Acta"},{"key":"ref26\/cit26c","doi-asserted-by":"crossref","first-page":"3124","DOI":"10.1021\/ja058550q","volume":"128","author":"Zhao P.","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref27\/cit27","doi-asserted-by":"crossref","first-page":"12066","DOI":"10.1021\/ja052473h","volume":"127","author":"Zhao P.","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"ref28\/cit28a","doi-asserted-by":"crossref","first-page":"760","DOI":"10.1002\/mrc.1437","volume":"42","author":"Carlton L.","year":"2004","journal-title":"Magn. Reson. Chem."}],"container-title":["Journal of the American Chemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/ja9005699","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,3,11]],"date-time":"2024-03-11T05:33:11Z","timestamp":1710135191000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/doi\/10.1021\/ja9005699"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2009,3,9]]},"references-count":41,"journal-issue":{"issue":"12","published-print":{"date-parts":[[2009,4,1]]}},"alternative-id":["10.1021\/ja9005699"],"URL":"https:\/\/doi.org\/10.1021\/ja9005699","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2009,3,9]]}}}