title: σ-π-Diauration as an alternative binding mode for digold intermediates in gold(i) catalysis.
abstract: While investigating the gold(i)-catalyzed intramolecular hydroarylation of allenes, the structure of a digoldvinyl intermediate was verified. Instead of the previously proposed geminally diaurated binding mode for the digold when L = PPh3, an alternative σ-π-diauration mode was observed with the bulkier ligand L = P(o-Tol)3. Reactivity studies indicate the σ-π-mode has a disproportionate effect on protonolysis reactivity.
authors.affiliation: Caudill Laboratories, Department of Chemistry, University of North Carolina at Chapel Hill, NC 27599, USA.
authors.forename: Dieter
authors.initials: D
authors.lastname: Weber
authors.forename: Michel R
authors.initials: MR
authors.lastname: Gagné
references.citation: Chem Soc Rev. 2011 Apr;40(4):1910-25
references.pmid: 21103517
references.citation: Chem Rev. 2008 Aug;108(8):3266-325
references.pmid: 18651778
references.citation: J Am Chem Soc. 2009 May 13;131(18):6350-1
references.pmid: 19368391
references.citation: Chem Rev. 2008 Aug;108(8):3239-65
references.pmid: 18613729
references.citation: Chem Rev. 2008 Aug;108(8):3351-78
references.pmid: 18652511
references.citation: Angew Chem Int Ed Engl. 2009;48(31):5733-6
references.pmid: 19562821
references.citation: J Am Chem Soc. 2012 May 30;134(21):9012-9
references.pmid: 22563621
references.citation: Angew Chem Int Ed Engl. 2012 Apr 27;51(18):4456-60
references.pmid: 22431399
references.citation: Chemistry. 2008;14(18):5382-91
references.pmid: 18442031
references.citation: Angew Chem Int Ed Engl. 2010 Nov 2;49(45):8466-70
references.pmid: 20718061
references.citation: Angew Chem Int Ed Engl. 2012 Aug 13;51(33):8156-9
references.pmid: 22811398
references.citation: Chem Rev. 2011 Mar 9;111(3):1994-2009
references.pmid: 21314182
references.citation: Angew Chem Int Ed Engl. 2012 Mar 5;51(10):2452-6
references.pmid: 22278847
references.citation: Chem Soc Rev. 2008 Sep;37(9):1766-75
references.pmid: 18762826
references.citation: J Am Chem Soc. 2012 Jun 6;134(22):9134-7
references.pmid: 22621418
references.citation: Chem Commun (Camb). 2010 Apr 7;46(13):2313-5
references.pmid: 20234943
references.citation: Chem Soc Rev. 2009 Nov;38(11):3208-21
references.pmid: 19847352
references.citation: Angew Chem Int Ed Engl. 2007;46(19):3410-49
references.pmid: 17427893
references.citation: Chem Soc Rev. 2012 Apr 21;41(8):3129-39
references.pmid: 22262401
references.citation: Chem Rev. 2011 Mar 9;111(3):1657-712
references.pmid: 21391565
references.citation: Chem Soc Rev. 2011 Mar;40(3):1358-67
references.pmid: 21103507
references.citation: Chem Rev. 2011 Mar 9;111(3):1954-93
references.pmid: 21391568
references.citation: Chem Commun (Camb). 2011 Jun 21;47(23):6536-44
references.pmid: 21451867
references.citation: Org Lett. 2009 Nov 5;11(21):4962-5
references.pmid: 19807117
references.citation: Org Lett. 2005 Sep 15;7(19):4133-6
references.pmid: 16146370
references.citation: Angew Chem Int Ed Engl. 2011 Mar 7;50(11):2628-31
references.pmid: 21370353
references.citation: Angew Chem Int Ed Engl. 2010 Jul 19;49(31):5232-41
references.pmid: 20572216
references.citation: Chem Rev. 2008 Aug;108(8):3326-50
references.pmid: 18636778
references.citation: Nature. 2007 Mar 22;446(7134):395-403
references.pmid: 17377576
references.citation: Angew Chem Int Ed Engl. 2006 Dec 4;45(47):7896-936
references.pmid: 17131371
references.citation: Angew Chem Int Ed Engl. 2012 Jun 11;51(24):5924-8
references.pmid: 22565395
references.citation: Chem Soc Rev. 2008 Sep;37(9):1931-51
references.pmid: 18762840
references.citation: Chem Rev. 2007 Jul;107(7):3180-211
references.pmid: 17580975