The activation of small molecules by transition metal complexes via ligand substitution or oxidative-addition has historically received a great deal of attention since these reactions are requisite for catalytic processes.  While chlorocarbonylbis(triphenylphosphine)iridium(I) (Vaska's compound) and some related isoelectronic and isostructural complexes of the type trans-[M(A)(CO)L2] (M = Ir, Rh;  A = anionic ligand; L = monodentate tertiary phosphine) have been examined in great detail, much less is known regarding the activation of small molecules by similar planar iridium(I) and rhodium(I) complexes containing bidentate alkyl or aryl phosphine ligands. Our work focused on the synthesis and reactivity of iridium complexes stabilized by the aryldiphosphine,  (C6H5)2PCH2P(C6H5)2, and the alkyl diphosphine, (C6H11)2PCH2P(C6H11)2.  We have prepared several covalent and ionic iridium-diphosphine-diene complexes which are capable of activating molecular hydrogen, hydrochloric acid and silanes resulting in some novel mono � and dihydride  complexes with retention of the diene ligand.  The solution structures of these complexes will be described.

Synthesis and characterization of low-valent iridium complexes stabilized by alkyl- and aryldiphosphines

247th National Meeting (2014)

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