Synthesis and structural characterization of new BINAP Ir(I) complexes disorder in CO, I and Ir (50:50)

experimental / simulated values Reaction of [Ir(CO)2(R-BINAP)][SbF6] with H2 shows diastereoselectivity Due to the chirality and C2 symmetry of the molecule, two diastereomers are formed experimental / simulated values kinetic diastereoselectivity equilibrium constant k1/k2 (k2 x k-1)/(k1 x k-2) 9 : 1 / 10.7 : 1 3.6 / 3.67 G‡ > 1.36 kcal/mol G298 = -0.81 kcal/mol

Diastereoselectivity of H2 addition to chiral IrI(CO)(R-BINAP) complex kinetic diastereomers form first with a high selectivity (> 99:1) most stable diastereomer favored by > 9:1 ratio over the other diastereomers kinetic diastereoselectivity equil. ratio of kin. isomers equil. ratio of ther. isomers experimental / simulated values 9 : 1 / 7.7 : 1 1.2 : 1 / 1.3 : 1 9 : 1 / 14 : 1 k1/k2 (k2 x k-1)/(k1 x k-2) (k4 x k-3)/(k3 x k-4)

Diastereoselectivity of H2 addition to chiral Ir(I) complexes seen using PHIP [Ir(CO)2(R-BINAP)][SbF6] + p-H2 IrI(CO)(R-BINAP) + p-H2 in both compounds, only the first formed isomer shows PHIP at RT the second formed isomers show PHIP at elevated temperatures occurrence of PHIP relates to rate of hydrogen cycling isomers having a hydride trans to -CO readily exchange with D2 at RT, while those with a hydride trans to iodide show no exchange at RT and only incomplete exchange after heating

Chiral BINAP Ir(III) complexes made and studied for catalysis catalysis of Nazarov cyclization seen Diels Alder catalysis; faster with DIB complex cationic rearrangement seen for Me2butadiene product

A tricationic complex has been found to have enhanced reactivity Nazarov cyclization catalysis seen for substrates not cyclized by the dicationic systems