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

2. 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 = kcal/mol

3. 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)

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

5. 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

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