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• W1973487182 endingPage "2729" @default.
• W1973487182 startingPage "2720" @default.
• W1973487182 abstract "A comparison between models for the substrate−catalyst adduct in hydrodenitrogenation (HDN) catalysis is made with respect to oxygen vs sulfur ancillary ligands. Reacting [η2(N,C)-NC5tBu3H2]Ta(OAr)2Cl (1, Ar = 2,6-C6H3iPr2) with KOtBu affords orange crystals of the alkoxide [η2(N,C)-NC5tBu3H2]Ta(OAr)2(OtBu) (2), while 1 and LiStBu react to form the red thiolate analogue [η2(N,C)-NC5tBu3H2]Ta(OAr)2(StBu) (3). Structural studies of both complexes 2 and 3 are reported and compared with other η2(N,C)-NC5tBu3H2 derivatives. A trace of the bromide complex [η2(N,C)-NC5tBu3H2]Ta(OAr)2Br (4) is isolated from reacting [η2(N,C)-NC5tBu3H2]Ta(OAr)2Cl (1) with EtMgBr in THF/Et2O solution and is also structurally characterized for comparison. Complexes 2−4 reveal a severe interruption of aromaticity within the heterocycle, different rotational preferences of the pyridine NC5 plane with respect to the Ta(OAr)2X moiety, and various aryloxide ligand structural differences. From this comparison, arguments will be presented that support the ancillary ligand π-donor ability decreasing as OtBu > OAr > StBu > Cl ≈ Br > Et, although evidence suggests that the StBu ligand is a better σ + π donor overall than OAr or OtBu." @default.
• W1973487182 created "2016-06-24" @default.
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• W1973487182 date "1998-06-01" @default.
• W1973487182 modified "2023-10-03" @default.
• W1973487182 title "Structural Models for the Substrate−Catalyst Adduct in Hydrodenitrogenation Catalysis: Oxygen vs Sulfur Ligation" @default.
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• W1973487182 doi "https://doi.org/10.1021/om970559g" @default.
• W1973487182 hasPublicationYear "1998" @default.
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