Reversible Ligand Protonation in Noninnocent Constrained-Geometry-Like Group 4 Complexes
Abstract
The proligands C5H5CMe2CHPhOxR (R = Me2, CHMe2, and CMe3) react with M(NMe2)4 (M = Ti, Zr, and Hf) to give monodeprotonated (OxRCHPhCMe2C5H4)M(NMe2)3, doubly deprotonated (C5H4CMe2CPhOxR)M(NMe2)2, or a mixture of both. The observed products depend on reaction conditions, the oxazoline substituent, and the metal center, with 4-t-butyl-oxazoline or Ti giving only the monodeprotonated (OxRCHPhCMe2C5H4)M(NMe2)3. Amine elimination from (OxRCHPhCMe2C5H4)M(NMe2)3 to give (C5H4CMe2CPhOxR)M(NMe2)2 is reversible for 4,4-dimethyl- and 4-isopropyl-oxazoline-based ligands in Zr or Hf complexes. Temperature-dependent kinetic studies of the equilibration of (C5H4CMe2CPhOxMe2)Zr(NMe2)2, HNMe2 and (OxMe2CHPhCMe2C5H4)Zr(NMe2)3 provide the experimental thermodynamic parameters ΔS° = -17.4 ± 2.6 cal·mol–1K–1 and ΔH° = -6.8 ± 0.8 kcal·mol–1. An Eyring plot of the rate constants, determined from the system as it approaches equilibrium, gives the activation entropy and activation enthalpy for the addition of (C5H4CMe2CPhOxMe2)Zr(NMe2)2 and HNMe2 as -36 ± 4 cal·mol–1 K–1 and 8.9 ± 1.3 kcal·mol–1, respectively; the elimination of HNMe2 from (OxMe2CHPhCMe2C5H4)Zr(NMe2)3 is characterized by ΔS‡ = -19 ± 5 cal·mol–1 K–1 and ΔH‡ = 15.7 ± 1.5 kcal·mol–1. DFT computational models indicate a single-step, nonlinear transfer of the H between the benzylic position of the noninnocent, oxazoline-coordinated ligand and NMe2. Computations also confirm the negative activation entropy and the trends in the barriersmore »
- Authors:
-
[1];
[1];
[1];
[1]
- Iowa State Univ., Ames, IA (United States); Ames Lab., and Iowa State Univ., Ames, IA (United States)
- Iowa State Univ., Ames, IA (United States)
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
- OSTI Identifier:
- 1842218
- Report Number(s):
- IS-J-10,691
Journal ID: ISSN 0276-7333
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Organometallics
- Additional Journal Information:
- Journal Volume: 41; Journal Issue: 2; Journal ID: ISSN 0276-7333
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; mixtures; chemical structure; molecular structure; alkyls; ligands
Citation Formats
Chu, Yang-Yun, Lolinco, Annabelle, Eedugurala, Naresh, Ellern, Arkady, Windus, Theresa L., and Sadow, Aaron D. Reversible Ligand Protonation in Noninnocent Constrained-Geometry-Like Group 4 Complexes. United States: N. p., 2022.
Web. doi:10.1021/acs.organomet.1c00612.
Chu, Yang-Yun, Lolinco, Annabelle, Eedugurala, Naresh, Ellern, Arkady, Windus, Theresa L., & Sadow, Aaron D. Reversible Ligand Protonation in Noninnocent Constrained-Geometry-Like Group 4 Complexes. United States. https://doi.org/10.1021/acs.organomet.1c00612
Chu, Yang-Yun, Lolinco, Annabelle, Eedugurala, Naresh, Ellern, Arkady, Windus, Theresa L., and Sadow, Aaron D. Thu .
"Reversible Ligand Protonation in Noninnocent Constrained-Geometry-Like Group 4 Complexes". United States. https://doi.org/10.1021/acs.organomet.1c00612. https://www.osti.gov/servlets/purl/1842218.
@article{osti_1842218,
title = {Reversible Ligand Protonation in Noninnocent Constrained-Geometry-Like Group 4 Complexes},
author = {Chu, Yang-Yun and Lolinco, Annabelle and Eedugurala, Naresh and Ellern, Arkady and Windus, Theresa L. and Sadow, Aaron D.},
abstractNote = {The proligands C5H5CMe2CHPhOxR (R = Me2, CHMe2, and CMe3) react with M(NMe2)4 (M = Ti, Zr, and Hf) to give monodeprotonated (OxRCHPhCMe2C5H4)M(NMe2)3, doubly deprotonated (C5H4CMe2CPhOxR)M(NMe2)2, or a mixture of both. The observed products depend on reaction conditions, the oxazoline substituent, and the metal center, with 4-t-butyl-oxazoline or Ti giving only the monodeprotonated (OxRCHPhCMe2C5H4)M(NMe2)3. Amine elimination from (OxRCHPhCMe2C5H4)M(NMe2)3 to give (C5H4CMe2CPhOxR)M(NMe2)2 is reversible for 4,4-dimethyl- and 4-isopropyl-oxazoline-based ligands in Zr or Hf complexes. Temperature-dependent kinetic studies of the equilibration of (C5H4CMe2CPhOxMe2)Zr(NMe2)2, HNMe2 and (OxMe2CHPhCMe2C5H4)Zr(NMe2)3 provide the experimental thermodynamic parameters ΔS° = -17.4 ± 2.6 cal·mol–1K–1 and ΔH° = -6.8 ± 0.8 kcal·mol–1. An Eyring plot of the rate constants, determined from the system as it approaches equilibrium, gives the activation entropy and activation enthalpy for the addition of (C5H4CMe2CPhOxMe2)Zr(NMe2)2 and HNMe2 as -36 ± 4 cal·mol–1 K–1 and 8.9 ± 1.3 kcal·mol–1, respectively; the elimination of HNMe2 from (OxMe2CHPhCMe2C5H4)Zr(NMe2)3 is characterized by ΔS‡ = -19 ± 5 cal·mol–1 K–1 and ΔH‡ = 15.7 ± 1.5 kcal·mol–1. DFT computational models indicate a single-step, nonlinear transfer of the H between the benzylic position of the noninnocent, oxazoline-coordinated ligand and NMe2. Computations also confirm the negative activation entropy and the trends in the barriers support the experimental results. Together, these studies indicate the importance of steric effects from the oxazoline ligand, metal center, ancillary ligands, and leaving group on the shuttling of the proton between HNMe2 and the noninnocent ligand. Finally, these effects suggest that coordination of oxazoline to the metal center is a key part of the benzylic deprotonation and noninnocent behavior of the cyclopentadienyl-oxazoline ligand.},
doi = {10.1021/acs.organomet.1c00612},
journal = {Organometallics},
number = 2,
volume = 41,
place = {United States},
year = {Thu Jan 06 00:00:00 EST 2022},
month = {Thu Jan 06 00:00:00 EST 2022}
}
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