Manuel A. Gomez?Bonilla, Verónica Salazar?Pereda, Daniel Mendoza?Espinosa, Simplicio Gonzalez?Montiel, Aracely Castañeda?Ovando, Susana Rojas?Lima, Cesar I. Sandoval?Chavez, Jorge A. Lopez?Jímenez. Reactivity of 2?mercaptopyridines with Iridium(I)?Tris(pyrazolyl) borate complexes. European Journal of Inorganic Chemistry, 2021, 13, 1244-1250. https://doi.org/10.1002/ejic.202001153
Reaction of of the Ir(I) complex [TpMe2Ir?(C2H4)2] (1) with a variety of mercaptopyridines produces in good yields the Ir(III)?metallacycles 2?4 with the general formula [TpMe2Ir(C2H5)(k2?(N,S)?mercaptopyridine)]. Complexes 2?4 are proposed to take place by the initial formation of the 16 electron intermediate [TpMe2Ir(CH=CH2)(C2H5)] which then coordinates the nitrogen atom of the mercaptopyridine and promotes the deprotonation of the SH group via the elimination of an ethylene molecule. Heating of complex [TpMe2Ir(?4?CH2=C(Me)C(Me)=CH2)]] (5) at 100?C with the substituted mercaptopyridines results in the formation of the Ir(III) complexes 6?8 with the general formula [TpMe2Ir(C6H5)(?2?(N,S)?mercaptopyridine)]. Generation of complexes 6?8 is proposed to take place by the initial formation of the [TpMe2Ir(C6H5)2N2] complex which after releasing nitrogen coordinates the mercaptopyridine in a ?1?fashion and favour the SH moiety deprotonation with the release of a benzene molecule. All complexes have been fully characterized by NMR spectroscopy, FT?IR, elemental analysis and in the case of 2, 4, and 8 by X?ray crystallography. Details of the reaction conditions, characterization and isolation of the products will be discussed.