pubs.acs.org/Organometallics Published on Web 11/24/2010 r 2010 American Chemical Society 6636 Organometallics 2010, 29, 6636–6638 DOI: 10.1021/om101005w Metalated-Arene-Phosphino Ligands: A Novel Approach to Open-Sided Gold Compounds M. Rosa Axet, Marion Barbazanges, Myl  ene Aug e, Christophe Desmarets, Jamal Moussa, Cyril Ollivier, Corinne Aubert,* Louis Fensterbank,* Vincent Gandon, ‡ Max Malacria, Lise Marie Chamoreau, and Hani Amouri* UPMC Universit e Paris 06, Institut Parisien de Chimie Mol eculaire (UMR CNRS 7201), 4 Place Jussieu, C. 42, 75252 Paris Cedex 05, France. ‡ Univ Paris-Sud, UMR CNRS 8182, Orsay 91405, France Received October 22, 2010 Summary: A novel type of metalated phosphino ligands, [Cp*Ru- (η 6 -arene-PPh 2 )][OTf](2a-d-OTf), has been prepared in which the -PPh 2 unit is attached to a metalated π-arene platform. This unique class of ligands 2a-d are converted to open-sided cationic gold complexes 3a-d upon treatment with [AuCl(tht)]. The structure of one of these compounds, [Cp*Ru(η 6 -C 6 H 5 -PPh 2 - Au-Cl )][OTf](3a-OTf), was ascertained by single-crystal X-ray diffraction. Preliminary studies suggest that cationic complex 3a is active in metal-catalyzed cycloisomerization reactions. Gold complexes have received much attention due to their importance in several applications such as luminescence, supramolecular chemistry, and nanoparticles, and more recently in catalysis. 1 Indeed in the past decade, homoge- neous gold catalysis has emerged as a powerful tool for novel organic transformations, thus providing a variety of C-C bond-forming reactions for the synthesis of complex chemi- cal structures. 2 In this context, efforts have been devoted to prepare new gold complexes by tuning the electronic and/or the steric properties of the donor ligand bound to the metal center, “LfAu” (L = PR 3 , carbenes, cyclic aminocarbene, etc.). 3,4 More recently Echavarren and co-workers designed a novel family of gold complexes with bulky phosphine ligands. 5 The latter showed enhanced catalytic activity com- pared to the market available [AuCl(PPh 3 )] complex. Pursuing our research in this area, we wish to report in this communication the design and synthesis of a novel family of gold complexes of the type L M fAu-Cl where L M is an organometallic phosphine ligand. In this ligand, the -PPh 2 moiety is now attached to a metalated π-arene platform (see Scheme 1). In this model complex, we sought to change the electronic and steric properties around the gold center in the hopes that this may lead to novel reactive species. To the best of our knowledge, this is the first example of such a com- pound to be reported in the literature. Our group has developed the synthesis of some neutral metalated π-quinones. The related reactive intermediates thioquinones and selenoquinones were also stabilized and isolated for the first time as π-complexes of “Cp*M” (M = Rh, Ir). 6 These π-quinonoid species were successfully used as organometallo ligands to prepare a variety of coordination assemblies and polymers with luminescent properties. 7 In this work we describe the synthesis of a new type of organo- metallo ligand where the phosphine moiety is attached to an arene complex of Cp*Ru. However we note that metalated phosphino ligands such as rigid phosphino-ferrocenes has been widely and successfully used in homogeneous catalysis by many groups. 8 *Corresponding authors. (H.A.) Fax: (33)1-44-27-38-41. E-mail: hani.amouri@upmc.fr. (C.A.) Fax: (33)1-44-27-73-60. E-mail: corinne.aubert@upmc.fr. (L.F.) Fax: (33)1-44-27-73-60. E-mail: louis. fensterbank@upmc.fr. (1) (a) Gold Chemistry: Applications and Future Directions in the Life Sciences; Mohr, F., Ed.; Wiley-VCH: Weinheim, 2009. 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