Solution structures of [IrH2(1,5‐cyclooctadiene) (bisphosphine)](CF3SO3) complexes. Homo‐ and heteronuclear long‐range couplings from hydride and phosphorus spins to cyclooctadiene protons

The solution structures of the two all‐cis stereoisomers of [IrH2(COD)((−)‐chiraphos)](CF3SO3) and the four all‐cis stereoisomers of [IrH2(COD)((−)‐norphos)](CF3SO3) [COD = cycloocta‐1,5‐diene, (−)‐chiraphos = 2S,3S‐bis(diphenyl‐ phosphino)butane, (−)‐norphos = 2R,3R‐bis(diphenylphosphino)norbornene] were assigned on the basis of various one‐ and two‐dimensional correlation methods. The rationalization of a specifically observed scalar coupling interaction between one of the hydrides and a methylene proton of the cyclooctadiene moiety required an assignment of all the relevant protons including their stereochemical relationship. Analogous long‐range coupling pathways were also found for the heteronuclear interactions nJ(P,H) and an interpretation of the origin of these scalar couplings is provided in the form of an expansion of the known geometric dependence of allylic and homoallylic couplings.