TY - JOUR
T1 - Lewis base adducts derived from transfer hydrogenation catalysts
T2 - Scope and selectivity
AU - Heiden, Zachariah M.
AU - Gorecki, Bradford J.
AU - Rauchfuss, Thomas
PY - 2008/4/14
Y1 - 2008/4/14
N2 - The coordination tendencies of the unsaturated 16e Lewis acid [Cp*Ir(TsDPEN)]+ ([1H]+), where TsDPEN is H 2NCHPhCHPhNTs-, are surveyed, together with parallel studies on analogous complexes such TsDACH (TsDACH = H2NC 6H10NTs-) and Tsen (Tsen = H2NC 2H4NTs-) derivatives as well as Rh analogues. Crystallographic analyses of the adducts of [Cp*IrL(TsDPEN)]+, where L = NCMe, NH3, PPh3, and CO, and [Cp*Ir(CO)(R,R-TsDACH)]+ are described. In the TsDPEN system, the Lewis base adducts contain an absolute configuration that is opposite that for the TsDPEN ligand and feature equatorial phenyl groups. In the case of [Cp*Ir(CO)(R,R-TsDACH)]+, both R and S metal centers cocrystallize. Isomerization of the R to the S metal center was first order in [Cp*(R-Ir)(CO)(R,R-TsDACH)]+ with minimal solvent effects. The pKa of the amine of the Lewis base adducts correlated linearly with the pKa of the free ligand in MeCN and the pKa of the amine (H2NCHPhCHPhNTs) of the Lewis base adduct in MeCN. Amines with pKa < 16 (MeCN scale), in the absence of additional hydrogen bonding to the TsDPEN ligand set, do not to bind to [1H]+, whereas bulky bases with pKa > 20 deprotonated the iridium amine.
AB - The coordination tendencies of the unsaturated 16e Lewis acid [Cp*Ir(TsDPEN)]+ ([1H]+), where TsDPEN is H 2NCHPhCHPhNTs-, are surveyed, together with parallel studies on analogous complexes such TsDACH (TsDACH = H2NC 6H10NTs-) and Tsen (Tsen = H2NC 2H4NTs-) derivatives as well as Rh analogues. Crystallographic analyses of the adducts of [Cp*IrL(TsDPEN)]+, where L = NCMe, NH3, PPh3, and CO, and [Cp*Ir(CO)(R,R-TsDACH)]+ are described. In the TsDPEN system, the Lewis base adducts contain an absolute configuration that is opposite that for the TsDPEN ligand and feature equatorial phenyl groups. In the case of [Cp*Ir(CO)(R,R-TsDACH)]+, both R and S metal centers cocrystallize. Isomerization of the R to the S metal center was first order in [Cp*(R-Ir)(CO)(R,R-TsDACH)]+ with minimal solvent effects. The pKa of the amine of the Lewis base adducts correlated linearly with the pKa of the free ligand in MeCN and the pKa of the amine (H2NCHPhCHPhNTs) of the Lewis base adduct in MeCN. Amines with pKa < 16 (MeCN scale), in the absence of additional hydrogen bonding to the TsDPEN ligand set, do not to bind to [1H]+, whereas bulky bases with pKa > 20 deprotonated the iridium amine.
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U2 - 10.1021/om700996m
DO - 10.1021/om700996m
M3 - Article
AN - SCOPUS:42449106096
SN - 0276-7333
VL - 27
SP - 1542
EP - 1549
JO - Organometallics
JF - Organometallics
IS - 7
ER -