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Rev."},{"key":"ref2\/cit2a","doi-asserted-by":"crossref","first-page":"15878","DOI":"10.1021\/ja036266y","volume":"125","author":"Hong S.","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"ref2\/cit2b","doi-asserted-by":"crossref","first-page":"8744","DOI":"10.1021\/ja0360539","volume":"125","author":"Trost B. M.","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"ref2\/cit2c","doi-asserted-by":"crossref","first-page":"4344","DOI":"10.1021\/jo015603n","volume":"66","author":"Molander G. A.","year":"2001","journal-title":"J. Org. Chem."},{"key":"ref2\/cit2d","doi-asserted-by":"crossref","first-page":"435","DOI":"10.1039\/a707613d","volume":"17","author":"O\u2019Hagan D.","year":"2000","journal-title":"Nat. Prod. Rep."},{"key":"ref2\/cit2e","doi-asserted-by":"crossref","first-page":"3633","DOI":"10.1021\/ja984305d","volume":"121","author":"Arredondo V. M.","year":"1999","journal-title":"J. Am. Chem. Soc."},{"key":"ref3\/cit3","unstructured":"For a selection of recent lead references, see:"},{"key":"ref3\/cit3a","doi-asserted-by":"crossref","first-page":"2423","DOI":"10.1021\/om9000023","volume":"28","author":"Yuen H. F.","year":"2009","journal-title":"Organometallics"},{"key":"ref3\/cit3b","doi-asserted-by":"crossref","first-page":"2318","DOI":"10.1021\/om900040r","volume":"28","author":"Lu E.","year":"2009","journal-title":"Organometallics"},{"key":"ref3\/cit3c","doi-asserted-by":"crossref","first-page":"2189","DOI":"10.1002\/chem.200701090","volume":"14","author":"Aillaud I.","year":"2008","journal-title":"Chem.\u2014Eur. J."},{"key":"ref3\/cit3d","doi-asserted-by":"crossref","first-page":"5339","DOI":"10.1021\/om8005382","volume":"27","author":"Ge S.","year":"2008","journal-title":"Organometallics"},{"key":"ref3\/cit3e","doi-asserted-by":"crossref","first-page":"3552","DOI":"10.1039\/b804745f","author":"Hannedouche J.","year":"2008","journal-title":"Chem. Commun."},{"key":"ref3\/cit3f","doi-asserted-by":"crossref","first-page":"1242","DOI":"10.1021\/om701058k","volume":"27","author":"Zi G.","year":"2008","journal-title":"Organometallics"},{"key":"ref3\/cit3g","doi-asserted-by":"crossref","first-page":"4253","DOI":"10.1021\/ja0665444","volume":"129","author":"Stubbert B. D.","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"ref3\/cit3h","doi-asserted-by":"crossref","first-page":"6149","DOI":"10.1021\/ja0675898","volume":"129","author":"Stubbert B. D.","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"ref3\/cit3i","doi-asserted-by":"crossref","first-page":"4690","DOI":"10.1016\/j.jorganchem.2007.05.010","volume":"692","author":"Vitanova D. V.","year":"2007","journal-title":"J. Organomet. Chem."},{"key":"ref3\/cit3j","doi-asserted-by":"crossref","first-page":"3606","DOI":"10.1002\/chem.200601510","volume":"13","author":"Rast\u00e4tter M.","year":"2007","journal-title":"Chem.\u2014Eur. J."},{"key":"ref3\/cit3k","doi-asserted-by":"crossref","first-page":"1159","DOI":"10.1002\/ejic.200600872","author":"Riegert D.","year":"2007","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref3\/cit3l","doi-asserted-by":"crossref","first-page":"365","DOI":"10.1021\/om0607999","volume":"26","author":"Yu X.","year":"2007","journal-title":"Organometallics"},{"key":"ref3\/cit3m","doi-asserted-by":"crossref","first-page":"874","DOI":"10.1039\/b514242c","author":"Rast\u00e4tter M.","year":"2006","journal-title":"Chem. Commun."},{"key":"ref3\/cit3n","doi-asserted-by":"crossref","first-page":"3748","DOI":"10.1021\/ja058287t","volume":"128","author":"Gribkov D. V.","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref3\/cit3o","doi-asserted-by":"crossref","first-page":"1157","DOI":"10.1039\/B512135C","author":"Bambirra S.","year":"2006","journal-title":"Dalton Trans."},{"key":"ref3\/cit3p","doi-asserted-by":"crossref","first-page":"4441","DOI":"10.1016\/j.jorganchem.2004.11.058","volume":"690","author":"Hultzsch K. C.","year":"2005","journal-title":"J. Organomet. Chem."},{"key":"ref3\/cit3q","doi-asserted-by":"crossref","first-page":"5205","DOI":"10.1039\/b505738h","author":"Kim H.","year":"2005","journal-title":"Chem. Commun."},{"key":"ref3\/cit3r","doi-asserted-by":"crossref","first-page":"4391","DOI":"10.1021\/ol051574h","volume":"7","author":"Kim J.-Y.","year":"2005","journal-title":"Org. Lett."},{"key":"ref3\/cit3s","doi-asserted-by":"crossref","first-page":"2234","DOI":"10.1021\/om0498551","volume":"23","author":"Lauterwasser F.","year":"2004","journal-title":"Organometallics"},{"key":"ref3\/cit3t","doi-asserted-by":"crossref","first-page":"673","DOI":"10.1021\/ar040051r","volume":"37","author":"Hong S.","year":"2004","journal-title":"Acc. Chem. Res."},{"key":"ref4\/cit4","unstructured":"For some recent references, see:"},{"key":"ref4\/cit4a","doi-asserted-by":"crossref","first-page":"3090","DOI":"10.1016\/j.tet.2008.09.045","volume":"65","author":"Zhang W.","year":"2009","journal-title":"Tetrahedron"},{"key":"ref4\/cit4b","doi-asserted-by":"crossref","first-page":"9670","DOI":"10.1021\/ja9003377","volume":"131","author":"Crimmin M. R.","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref4\/cit4c","doi-asserted-by":"crossref","first-page":"1730","DOI":"10.1021\/om8010933","volume":"28","author":"Arrowsmith M.","year":"2009","journal-title":"Organometallics"},{"key":"ref4\/cit4d","doi-asserted-by":"crossref","first-page":"1207","DOI":"10.1021\/om701014d","volume":"27","author":"Datta S.","year":"2008","journal-title":"Organometallics"},{"key":"ref4\/cit4e","doi-asserted-by":"crossref","first-page":"2221","DOI":"10.1039\/B518360J","author":"Martinez P. H.","year":"2006","journal-title":"Chem. Commun."},{"key":"ref5\/cit5","unstructured":"For a selection of recent lead references, see:"},{"key":"ref5\/cit5a","first-page":"97","author":"Lee A. V.","year":"2009","journal-title":"Synthesis"},{"key":"ref5\/cit5b","doi-asserted-by":"crossref","first-page":"429","DOI":"10.1002\/ejic.200800977","author":"Lian B.","year":"2009","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref5\/cit5c","doi-asserted-by":"crossref","first-page":"5001","DOI":"10.1039\/b805174g","author":"Cho J.","year":"2008","journal-title":"Chem. Commun."},{"key":"ref5\/cit5d","doi-asserted-by":"crossref","first-page":"1135","DOI":"10.1002\/ejic.200701105","author":"Xiang L.","year":"2008","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref5\/cit5e","doi-asserted-by":"crossref","first-page":"1174","DOI":"10.1021\/om700883a","volume":"27","author":"Majumder S.","year":"2008","journal-title":"Organometallics"},{"key":"ref5\/cit5f","doi-asserted-by":"crossref","first-page":"354","DOI":"10.1002\/anie.200603017","volume":"46","author":"Wood M. C.","year":"2007","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref5\/cit5g","first-page":"2243","author":"Lee A. V.","year":"2007","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref5\/cit5h","doi-asserted-by":"crossref","first-page":"1729","DOI":"10.1021\/om061087l","volume":"26","author":"Gott A. L.","year":"2007","journal-title":"Organometallics"},{"key":"ref5\/cit5i","doi-asserted-by":"crossref","first-page":"2499","DOI":"10.1002\/ejoc.200600115","author":"M\u00fcller C.","year":"2006","journal-title":"Eur. J. Org. Chem."},{"key":"ref5\/cit5j","doi-asserted-by":"crossref","first-page":"4731","DOI":"10.1021\/om0606791","volume":"25","author":"Watson D. A.","year":"2006","journal-title":"Organometallics"},{"key":"ref5\/cit5k","doi-asserted-by":"crossref","first-page":"894","DOI":"10.1039\/b401493f","author":"Knight P. D.","year":"2004","journal-title":"Chem. Commun."},{"key":"ref6\/cit6a","doi-asserted-by":"crossref","first-page":"1975","DOI":"10.1039\/B706301F","volume":"5","author":"Ackermann L.","year":"2007","journal-title":"Org. Biomol. Chem."},{"key":"ref6\/cit6b","doi-asserted-by":"crossref","first-page":"1471","DOI":"10.1021\/ol025659j","volume":"4","author":"Schlummer B.","year":"2002","journal-title":"Org. Lett."},{"key":"ref7\/cit7","doi-asserted-by":"crossref","first-page":"2938","DOI":"10.1002\/anie.200503789","volume":"45","author":"Komeyama K.","year":"2006","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref8\/cit8a","doi-asserted-by":"crossref","first-page":"2786","DOI":"10.1021\/ja0734997","volume":"130","author":"Cochran B. M.","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref8\/cit8b","doi-asserted-by":"crossref","first-page":"329","DOI":"10.1021\/ol702891p","volume":"10","author":"Cochran B. M.","year":"2008","journal-title":"Org. Lett."},{"key":"ref8\/cit8c","doi-asserted-by":"crossref","first-page":"4246","DOI":"10.1021\/ja060126h","volume":"128","author":"Michael F. E.","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref9\/cit9a","doi-asserted-by":"crossref","first-page":"4143","DOI":"10.1039\/b608638a","author":"Bender C. F.","year":"2006","journal-title":"Chem. Commun."},{"key":"ref9\/cit9b","doi-asserted-by":"crossref","first-page":"5303","DOI":"10.1021\/ol062107i","volume":"8","author":"Bender C. F.","year":"2006","journal-title":"Org. Lett."},{"key":"ref9\/cit9c","doi-asserted-by":"crossref","first-page":"1798","DOI":"10.1021\/ja053864z","volume":"128","author":"Zhang J.","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref9\/cit9d","doi-asserted-by":"crossref","first-page":"2707","DOI":"10.1021\/ol060719x","volume":"8","author":"Liu X.-Y.","year":"2006","journal-title":"Org. Lett."},{"key":"ref9\/cit9e","doi-asserted-by":"crossref","first-page":"1747","DOI":"10.1002\/anie.200600052","volume":"45","author":"Han X.","year":"2006","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref10\/cit10","unstructured":"The Au-catalyzed intermolecular hydroamination of simple \u03b1-olefins with cyclic ureas has been reported recently:"},{"key":"ref10\/cit10a","doi-asserted-by":"crossref","first-page":"5372","DOI":"10.1021\/ja9001162","volume":"131","author":"Zhang Z.","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref11\/cit11a","doi-asserted-by":"crossref","first-page":"1070","DOI":"10.1021\/ja043278q","volume":"127","author":"Bender C. F.","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"ref11\/cit11b","doi-asserted-by":"crossref","first-page":"2356","DOI":"10.1021\/om8000982","volume":"27","author":"Bender C. F.","year":"2008","journal-title":"Organometallics"},{"key":"ref12\/cit12","doi-asserted-by":"crossref","first-page":"1570","DOI":"10.1021\/ja710126x","volume":"130","author":"Liu Z.","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref13\/cit13","doi-asserted-by":"crossref","first-page":"1175","DOI":"10.1021\/ol8000766","volume":"10","author":"Bauer E. B.","year":"2008","journal-title":"Org. Lett."},{"key":"ref14\/cit14","unstructured":"For our preliminary report of the use of [Ir(COD)Cl]2as a pre-catalyst for the intramolecular hydroamination of secondary alkyl- or arylamines (but not primary amines) and unactivated olefins, see:"},{"key":"ref14\/cit14a","doi-asserted-by":"crossref","first-page":"1449","DOI":"10.1021\/ol900174f","volume":"11","author":"Hesp K. D.","year":"2009","journal-title":"Org. Lett."},{"key":"ref15\/cit15","doi-asserted-by":"crossref","first-page":"2145","DOI":"10.1021\/ol9007712","volume":"11","author":"Ohmiya H.","year":"2009","journal-title":"Org. Lett."},{"key":"ref16\/cit16","unstructured":"Dorta, R.InIridium Complexes in Organic Synthesis;Oro, L. A. and Claver, C., Eds.Wiley-VCH:Weinheim, 2009; p145."},{"key":"ref17\/cit17a","doi-asserted-by":"crossref","first-page":"6738","DOI":"10.1021\/ja00228a022","volume":"110","author":"Casalnuovo A. L.","year":"1988","journal-title":"J. Am. Chem. Soc."},{"key":"ref17\/cit17b","doi-asserted-by":"crossref","first-page":"10857","DOI":"10.1021\/ja972594k","volume":"119","author":"Dorta R.","year":"1997","journal-title":"J. Am. Chem. Soc."},{"key":"ref18\/cit18","doi-asserted-by":"crossref","first-page":"12220","DOI":"10.1021\/ja803523z","volume":"130","author":"Zhou J.","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref19\/cit19","unstructured":"For some recent reports, see:"},{"key":"ref19\/cit19a","doi-asserted-by":"crossref","first-page":"3599","DOI":"10.1039\/b821188d","author":"Field L. D.","year":"2009","journal-title":"Dalton Trans."},{"key":"ref19\/cit19b","doi-asserted-by":"crossref","first-page":"817","DOI":"10.1039\/b719501j","author":"Ebrahimi D.","year":"2008","journal-title":"Analyst"},{"key":"ref19\/cit19c","doi-asserted-by":"crossref","first-page":"4335","DOI":"10.1021\/om700428q","volume":"26","author":"Burling S.","year":"2007","journal-title":"Organometallics"},{"key":"ref19\/cit19d","doi-asserted-by":"crossref","first-page":"1062","DOI":"10.1021\/om060965c","volume":"26","author":"Lai R.-Y.","year":"2007","journal-title":"Organometallics"},{"key":"ref19\/cit19e","doi-asserted-by":"crossref","first-page":"5437","DOI":"10.1021\/ol052186i","volume":"7","author":"Li X.","year":"2005","journal-title":"Org. Lett."},{"key":"ref20\/cit20a","doi-asserted-by":"crossref","first-page":"2741","DOI":"10.1039\/b804081h","author":"Bender C. F.","year":"2008","journal-title":"Chem. Commun."},{"key":"ref20\/cit20b","doi-asserted-by":"crossref","first-page":"489","DOI":"10.1016\/S1381-1169(01)00496-4","volume":"182","author":"Penzien J.","year":"2002","journal-title":"J. Mol. Catal., A"},{"key":"ref20\/cit20c","doi-asserted-by":"crossref","first-page":"4384","DOI":"10.1021\/om010524n","volume":"20","author":"M\u00fcller T. E.","year":"2001","journal-title":"Organometallics"},{"key":"ref21\/cit21","doi-asserted-by":"crossref","first-page":"853","DOI":"10.1021\/ja073578i","volume":"130","author":"Kov\u00e1cs G.","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref22\/cit22a","doi-asserted-by":"crossref","first-page":"8134","DOI":"10.1021\/ja061349a","volume":"128","author":"Sakai N.","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref22\/cit22b","doi-asserted-by":"crossref","first-page":"1828","DOI":"10.1021\/ja056003z","volume":"128","author":"Johns A. M.","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref22\/cit22c","doi-asserted-by":"crossref","first-page":"3669","DOI":"10.1021\/ja017575w","volume":"124","author":"Pawlas J.","year":"2002","journal-title":"J. Am. Chem. Soc."},{"key":"ref22\/cit22d","doi-asserted-by":"crossref","first-page":"2469","DOI":"10.1021\/ol049137a","volume":"6","author":"Vo L. K.","year":"2004","journal-title":"Org. Lett."},{"key":"ref22\/cit22e","doi-asserted-by":"crossref","first-page":"1166","DOI":"10.1021\/ja017521m","volume":"124","author":"Nettekoven U.","year":"2002","journal-title":"J. Am. Chem. Soc."},{"key":"ref23\/cit23","doi-asserted-by":"crossref","first-page":"5756","DOI":"10.1021\/ja0506410","volume":"127","author":"Takaya J.","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"ref24\/cit24","doi-asserted-by":"crossref","first-page":"16562","DOI":"10.1021\/ja8030104","volume":"130","author":"McBee J. L.","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref25\/cit25a","doi-asserted-by":"crossref","first-page":"111","DOI":"10.1039\/B715507G","author":"Leighton-Munro C.","year":"2008","journal-title":"Chem. Commun."},{"key":"ref25\/cit25b","doi-asserted-by":"crossref","first-page":"1483","DOI":"10.1021\/om061133h","volume":"26","author":"Leighton-Munro C.","year":"2007","journal-title":"Organometallics"},{"key":"ref26\/cit26","doi-asserted-by":"crossref","first-page":"4949","DOI":"10.1002\/anie.200501150","volume":"44","author":"Genin E.","year":"2005","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref27\/cit27","unstructured":"Anslyn, E. V. and Dougherty, D. A.Modern Physical Organic Chemistry,1st ed.University Science Books:Sausalito, 2006; p372."},{"key":"ref28\/cit28","unstructured":"For a computational study of group 8 metal-assisted intermolecular hydroamination, see:"},{"key":"ref28\/cit28a","doi-asserted-by":"crossref","first-page":"4098","DOI":"10.1021\/ja992689h","volume":"122","author":"Senn H. M.","year":"2000","journal-title":"J. Am. Chem. Soc."},{"key":"ref28\/cit28b","doi-asserted-by":"crossref","first-page":"1696","DOI":"10.1021\/om0509342","volume":"25","author":"Tsipis C. A.","year":"2006","journal-title":"Organometallics"},{"key":"ref28\/cit28c","doi-asserted-by":"crossref","first-page":"5245","DOI":"10.1016\/j.jorganchem.2007.08.007","volume":"692","author":"Tsipis C. A.","year":"2007","journal-title":"J. Organomet. Chem."},{"key":"ref29\/cit29","unstructured":"For a computational study of group 4 metal-assisted intermolecular hydroamination, see:"},{"key":"ref29\/cit29a","doi-asserted-by":"crossref","first-page":"4632","DOI":"10.1002\/1521-3773(20011217)40:24<4632::AID-ANIE4632>3.0.CO;2-V","volume":"40","author":"Straub B. F.","year":"2001","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref30\/cit30","unstructured":"For computational studies of group 4 transition metal-assisted intramolecular hydroamination of various substrate classes, see: aminoalkene substrates:"},{"key":"ref30\/cit30a","doi-asserted-by":"crossref","first-page":"10430.","DOI":"10.1002\/chem.200801445","volume":"14","author":"M\u00fcller C.","year":"2008","journal-title":"Chem.\u2212Eur. J."},{"key":"ref30\/cit30b","doi-asserted-by":"crossref","first-page":"4277","DOI":"10.1039\/b605992a","author":"Tobisch S.","year":"2006","journal-title":"Dalton Trans."},{"key":"ref30\/cit30c","doi-asserted-by":"crossref","first-page":"4884","DOI":"10.1002\/chem.200601287","volume":"13","author":"Tobisch S.","year":"2007","journal-title":"Chem.\u2014Eur. J."},{"key":"ref30\/cit30d","doi-asserted-by":"crossref","first-page":"8590","DOI":"10.1002\/chem.200800750","volume":"14","author":"Tobisch S.","year":"2008","journal-title":"Chem.\u2014Eur. J."},{"key":"ref31\/cit31","unstructured":"For computational studies of organolanthanide-assisted intramolecular hydroamination of various substrate classes, see: aminoalkene substrates:"},{"key":"ref31\/cit31a","doi-asserted-by":"crossref","first-page":"4097.","DOI":"10.1021\/om049666i","volume":"23","author":"Motta A.","year":"2004","journal-title":"Organometallics"},{"key":"ref31\/cit31b","doi-asserted-by":"crossref","first-page":"5533","DOI":"10.1021\/om060717g","volume":"25","author":"Motta A.","year":"2006","journal-title":"Organometallics"},{"key":"ref31\/cit31c","doi-asserted-by":"crossref","first-page":"2520","DOI":"10.1002\/chem.200501017","volume":"12","author":"Tobisch S.","year":"2006","journal-title":"Chem.\u2014Eur. J."},{"key":"ref31\/cit31d","doi-asserted-by":"crossref","first-page":"11979","DOI":"10.1021\/ja042546h","volume":"127","author":"Tobisch S.","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"ref31\/cit31e","doi-asserted-by":"crossref","first-page":"9127","DOI":"10.1002\/chem.200700616","volume":"13","author":"Tobisch S.","year":"2007","journal-title":"Chem.\u2014Eur. J."},{"key":"ref32\/cit32","unstructured":"For a selection of lead references for the olefin activation route, see:"},{"key":"ref32\/cit32a","doi-asserted-by":"crossref","first-page":"2523","DOI":"10.1246\/bcsj.47.2523","volume":"47","author":"Kiji J.","year":"1974","journal-title":"Bull. Chem. Soc. Jpn."},{"key":"ref32\/cit32b","doi-asserted-by":"crossref","first-page":"255","DOI":"10.1016\/S0022-328X(00)85753-8","volume":"181","author":"Armb\u00fcchl J.","year":"1979","journal-title":"J. Organomet. Chem."},{"key":"ref32\/cit32c","doi-asserted-by":"crossref","first-page":"744","DOI":"10.1021\/om00027a026","volume":"12","author":"Seligson A. L.","year":"1993","journal-title":"Organometallics"},{"key":"ref32\/cit32d","first-page":"9646","volume":"122","author":"Kwatsura M.","year":"2000","journal-title":"J. Am. Chem. Soc."},{"key":"ref32\/cit32e","doi-asserted-by":"crossref","first-page":"170","DOI":"10.1021\/om9906013","volume":"1","author":"M\u00fcller T. E.","year":"2000","journal-title":"Organometallics"},{"key":"ref32\/cit32f","doi-asserted-by":"crossref","first-page":"1153","DOI":"10.1039\/b108234p","author":"Seul J. M.","year":"2002","journal-title":"J. Chem. Soc., Dalton Trans."},{"key":"ref32\/cit32g","doi-asserted-by":"crossref","first-page":"12640","DOI":"10.1021\/ja052836d","volume":"127","author":"Karshtedt D.","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"ref32\/cit32h","unstructured":"hReferences19eand20cherein."},{"key":"ref33\/cit33","unstructured":"For a selection of lead references for the amine activation route, see:"},{"key":"ref33\/cit33a","doi-asserted-by":"crossref","first-page":"971","DOI":"10.1021\/ic00254a001","volume":"26","author":"Casalnuovo A. L.","year":"1987","journal-title":"Inorg. Chem."},{"key":"ref33\/cit33b","doi-asserted-by":"crossref","first-page":"2451","DOI":"10.1021\/om00154a031","volume":"6","author":"Cowan R. L.","year":"1987","journal-title":"Organometallics"},{"key":"ref33\/cit33c","doi-asserted-by":"crossref","first-page":"1700","DOI":"10.1021\/om00109a020","volume":"8","author":"Park S.","year":"1989","journal-title":"Organometallics"},{"key":"ref33\/cit33d","doi-asserted-by":"crossref","first-page":"4127","DOI":"10.1021\/ic00346a003","volume":"29","author":"Ladipo F. T.","year":"1990","journal-title":"Inorg. Chem."},{"key":"ref33\/cit33e","doi-asserted-by":"crossref","first-page":"707","DOI":"10.1002\/anie.199107071","volume":"30","author":"Koelliker R.","year":"1991","journal-title":"Angew. Chem., Int. Ed. Engl."},{"key":"ref33\/cit33f","first-page":"1461","volume":"10","author":"Glueck D. S.","year":"1991","journal-title":"Organometallics"},{"key":"ref33\/cit33g","doi-asserted-by":"crossref","first-page":"3371","DOI":"10.1021\/ic00018a003","volume":"30","author":"Seligson A. L.","year":"1991","journal-title":"Inorg. Chem."},{"key":"ref33\/cit33h","unstructured":"hReferences16\u221218herein."},{"key":"ref34\/cit34","unstructured":"See theSupporting Informationfor more detail."},{"key":"ref35\/cit35","unstructured":"The activation energy for fragmentation ofM0has not been assessed, but it is rather unlikely to invoke any significant barrier, as the examination by a linear-transit approach gave no indication for the existence of such a barrier."},{"key":"ref36\/cit36","unstructured":"Examination by a linear-transit approach gave no indication that this process is associated with a substantial enthalpy barrier."},{"key":"ref37\/cit37","unstructured":"This was done by employing a discrete ensemble of three molecules of 1,4-dioxane closely interacting with the Cl center, thereby simulating specific solvation effects adequately."},{"key":"ref38\/cit38","unstructured":"The various conformers of the zwitterionic intermediateM2are in rapid equilibrium, as mutual interconversion does not impose any substantial barrier due to almost free rotation of the azacycle unit around Ir\u2212C and C\u2212C bonds inM2."},{"key":"ref39\/cit39","unstructured":"We have not determined the barrier for skeletal (polytopal) rearrangement between different forms ofM3, but such processes are known to be facile."},{"key":"ref40\/cit40","unstructured":"DFT predicts a kinetic gap of 11.9 kcal mol\u22121(\u0394\u0394G\u29e7) between stepwise protonolysis of the Ir\u2212C bond and \u03b2-hydride elimination commencing fromM2, in favor of the former, which leads us to confidently conclude that \u03b2-hydride elimination is not traversable."},{"key":"ref41\/cit41","unstructured":"Note that the barriers for mutual interconversion via Berry rotation are generally considered to be low."},{"key":"ref42\/cit42a","unstructured":"aThe absolute TOF-determining barrier is given relative to the catalyst resting stateM1a."},{"key":"ref42\/cit42b","unstructured":"bDFT predicts that DBU binds more strongly in [Ir(COD)Cl(amine)] compounds than1adoes inM1aby 12.0 kcal mol\u22121. On the other hand, the aminoalkene1adisplaces pyrrolidine2afromM4bin a kinetically viable, downhill step (see Figure7)."},{"key":"ref42\/cit42c","unstructured":"cCyclohydroamination of1ato2ahas an observed turnover-limiting barrier of 27.7 kcal mol\u22121(\u0394G\u29e7, 298 K)."},{"key":"ref43\/cit43","doi-asserted-by":"crossref","first-page":"1553","DOI":"10.1039\/c29700001553","author":"Green M.","year":"1970","journal-title":"Chem. Commun."},{"key":"ref44\/cit44","doi-asserted-by":"crossref","first-page":"10388","DOI":"10.1002\/chem.200801530","volume":"14","author":"Lundgren R. J.","year":"2008","journal-title":"Chem.\u2014Eur. J."},{"key":"ref45\/cit45","doi-asserted-by":"crossref","first-page":"2033","DOI":"10.1021\/ja00293a038","volume":"107","author":"Auburn P. R.","year":"1985","journal-title":"J. Am. Chem. Soc."},{"key":"ref46\/cit46","doi-asserted-by":"crossref","first-page":"1174","DOI":"10.1021\/om700883a","volume":"27","author":"Majumder S.","year":"2008","journal-title":"Organometallics"},{"key":"ref47\/cit47","doi-asserted-by":"crossref","first-page":"3405","DOI":"10.1039\/B607597E","author":"Dochnahl M.","year":"2006","journal-title":"Chem. Commun."},{"key":"ref48\/cit48","author":"Lundgren R. J.","journal-title":"Chem.\u2014Eur. J"},{"key":"ref49\/cit49","volume-title":"Density-Functional Theory of Atoms and Molecules","author":"Parr R. G.","year":"1989"},{"key":"ref50\/cit50a","doi-asserted-by":"crossref","first-page":"165","DOI":"10.1016\/0009-2614(89)85118-8","volume":"162","author":"Ahlrichs R.","year":"1989","journal-title":"Chem. Phys. Lett."},{"key":"ref50\/cit50b","doi-asserted-by":"crossref","first-page":"346","DOI":"10.1063\/1.469408","volume":"102","author":"Treutler O.","year":"1995","journal-title":"J. Chem. Phys."},{"key":"ref50\/cit50c","volume-title":"TURBOMOLE, version 6.0","author":"Ahlrichs R."},{"key":"ref51\/cit51a","first-page":"714","volume":"123","author":"Dirac P. A. M.","year":"1929","journal-title":"Proc. R. Soc. London"},{"key":"ref51\/cit51b","doi-asserted-by":"crossref","first-page":"385","DOI":"10.1103\/PhysRev.81.385","volume":"81","author":"Slater J. C.","year":"1951","journal-title":"Phys. Rev."},{"key":"ref51\/cit51c","doi-asserted-by":"crossref","first-page":"13244","DOI":"10.1103\/PhysRevB.45.13244","volume":"45","author":"Perdew J. P.","year":"1992","journal-title":"Phys. Rev."},{"key":"ref51\/cit51d","doi-asserted-by":"crossref","first-page":"146401","DOI":"10.1103\/PhysRevLett.91.146401","volume":"91","author":"Tao J.","year":"2003","journal-title":"Phys. Rev. Lett."},{"key":"ref51\/cit51e","doi-asserted-by":"crossref","first-page":"6898","DOI":"10.1063\/1.1665298","volume":"120","author":"Perdew J. P.","year":"2004","journal-title":"J. Chem. Phys."},{"key":"ref52\/cit52a","doi-asserted-by":"crossref","first-page":"514","DOI":"10.1016\/0009-2614(93)89151-7","volume":"213","author":"Vahtras O.","year":"1993","journal-title":"Chem. Phys. Lett."},{"key":"ref52\/cit52b","doi-asserted-by":"crossref","first-page":"652","DOI":"10.1016\/0009-2614(95)00838-U","volume":"242","author":"Eichkorn K.","year":"1995","journal-title":"Chem. Phys. Lett."},{"key":"ref53\/cit53","doi-asserted-by":"crossref","first-page":"123","DOI":"10.1007\/BF01114537","volume":"77","author":"Andrae D.","year":"1990","journal-title":"Theor. Chim. Acta"},{"key":"ref54\/cit54a","doi-asserted-by":"crossref","first-page":"3297","DOI":"10.1039\/b508541a","volume":"7","author":"Weigend F.","year":"2005","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref54\/cit54b","doi-asserted-by":"crossref","first-page":"1057","DOI":"10.1039\/b515623h","volume":"8","author":"Weigend F.","year":"2006","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref55\/cit55a","doi-asserted-by":"crossref","first-page":"5829","DOI":"10.1063\/1.467146","volume":"100","author":"Sch\u00e4fer A.","year":"1994","journal-title":"J. Chem. Phys."},{"key":"ref55\/cit55b","doi-asserted-by":"crossref","first-page":"119","DOI":"10.1007\/s002140050244","volume":"97","author":"Eichkorn K.","year":"1997","journal-title":"Theor. Chem. Acc."},{"key":"ref56\/cit56a","doi-asserted-by":"crossref","first-page":"12129","DOI":"10.1063\/1.1626543","volume":"119","author":"Staroverov V. N.","year":"2003","journal-title":"J. Chem. Phys."},{"key":"ref56\/cit56b","doi-asserted-by":"crossref","first-page":"415","DOI":"10.1021\/ct049851d","volume":"1","author":"Zao Y.","year":"2005","journal-title":"J. Chem. Theory Comput."},{"key":"ref56\/cit56c","doi-asserted-by":"crossref","first-page":"044103","DOI":"10.1063\/1.2162161","volume":"124","author":"Furche F.","year":"2006","journal-title":"J. Chem. Phys."},{"key":"ref57\/cit57","doi-asserted-by":"crossref","first-page":"799","DOI":"10.1039\/P29930000799","author":"Klamt A.","year":"1993","journal-title":"J. Chem. Soc., Perkin Trans 2"},{"key":"ref58\/cit58","unstructured":"For further details, seehttp:\/\/www.struked.de."}],"container-title":["Journal of the American Chemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/ja908316n","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,3,5]],"date-time":"2023-03-05T11:37:34Z","timestamp":1678016254000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/doi\/10.1021\/ja908316n"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2009,12,9]]},"references-count":178,"journal-issue":{"issue":"1","published-print":{"date-parts":[[2010,1,13]]}},"alternative-id":["10.1021\/ja908316n"],"URL":"https:\/\/doi.org\/10.1021\/ja908316n","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2009,12,9]]}}}