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- W2000450671 abstract "The coordination tendencies of the unsaturated 16e Lewis acid [Cp*Ir(TsDPEN)]+ ([1H]+), where TsDPEN is H2NCHPhCHPhNTs−, are surveyed, together with parallel studies on analogous complexes such TsDACH (TsDACH = H2NC6H10NTs−) and Tsen (Tsen = H2NC2H4NTs−) 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." @default.
- W2000450671 created "2016-06-24" @default.
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- W2000450671 date "2008-03-13" @default.
- W2000450671 modified "2023-10-17" @default.
- W2000450671 title "Lewis Base Adducts Derived from Transfer Hydrogenation Catalysts: Scope and Selectivity" @default.
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- W2000450671 doi "https://doi.org/10.1021/om700996m" @default.
- W2000450671 hasPublicationYear "2008" @default.
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