Controlling P–C/C–H Bond Cleavage in Nickel Bis(diphosphine) Complexes: Reactivity Scope, Mechanism, and Computations
Abstract
The synthesis of heteroleptic [Ni(P2N2)(diphosphine)][BF4]2 complexes and the cleavage of P–C and C–H bonds of the P2N2 ligand in those complexes are reported here. The products are five-coordinate complexes in which Ni–C and P–H bonds have formed to give a cyclic moiety containing Ni–CH$$=$$NR2. The reactivity of [Ni(P2N2)(diphosphine)][BF4]2 complexes is influenced by the rigidity of the diphosphine, the steric effect of the substituents, and length of the carbon linker of the diphosphine ligands. Diphosphine ligands bearing a rigid backbone (e.g., dmpbz, 1,2-bis(dimethylphosphino)benzene) or aromatic substituents (e.g., dppe, 1,2-bis(diphenylphosphino)ethane) react with [Ni(PtBu2NBn2)(CH3CN)2][BF4]2 to give P–C/C–H bond cleavage products. Both [Ni(PtBu2NBn2)(dmpe)(MeCN)][BF4]2 and [Ni(PtBu2NBn2)(dmpm)(MeCN)][BF4]2 (dmpm = 1,2-bis(dimethylylphosphino)methane) were prepared by the reaction of [Ni(PtBu2NBn2)(CH3CN)2][BF4]2 with the corresponding diphosphine ligands. [Ni(PtBu2NBn2)(dmpe)(MeCN)][BF4]2 readily undergoes P–C/C–H bond cleavage in nitromethane. In sharp contrast, [Ni(PtBu2NBn2)(dmpm)][BF4]2 is stabilized by dmpm, a diphosphine with small bite angle, and does not show P–C/C–H bond cleavage reactivity. Computational results show that for complexes bearing less bulky diphosphine ligands, such as dmpm, the barriers for the rate-determining transition states are in some examples higher than 30 kcal/mol with the M06 functional, higher than those for complexes bearing more rigid or more bulky ligands, consistent with experimental studies. The calculated barriers for the first transition state correlated with increased values of the dihedral angle formed by the two NiP2 planes.
- Authors:
-
[1];
[1];
[2];
[1]
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis
- Texas A & M Univ., College Station, TX (United States)
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); Welch Foundation
- OSTI Identifier:
- 1682269
- Report Number(s):
- PNNL-SA-140527
Journal ID: ISSN 0276-7333
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Organometallics
- Additional Journal Information:
- Journal Volume: 39; Journal Issue: 18; Journal ID: ISSN 0276-7333
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ligands; Bond cleavage; Organophosphorus compounds; Reactivity; Mathematical methods
Citation Formats
Zhang, Shaoguang, Li, Haixia, Appel, Aaron M., Hall, Michael B., and Bullock, R. Morris. Controlling P–C/C–H Bond Cleavage in Nickel Bis(diphosphine) Complexes: Reactivity Scope, Mechanism, and Computations. United States: N. p., 2020.
Web. doi:10.1021/acs.organomet.0c00388.
Zhang, Shaoguang, Li, Haixia, Appel, Aaron M., Hall, Michael B., & Bullock, R. Morris. Controlling P–C/C–H Bond Cleavage in Nickel Bis(diphosphine) Complexes: Reactivity Scope, Mechanism, and Computations. United States. https://doi.org/10.1021/acs.organomet.0c00388
Zhang, Shaoguang, Li, Haixia, Appel, Aaron M., Hall, Michael B., and Bullock, R. Morris. Thu .
"Controlling P–C/C–H Bond Cleavage in Nickel Bis(diphosphine) Complexes: Reactivity Scope, Mechanism, and Computations". United States. https://doi.org/10.1021/acs.organomet.0c00388. https://www.osti.gov/servlets/purl/1682269.
@article{osti_1682269,
title = {Controlling P–C/C–H Bond Cleavage in Nickel Bis(diphosphine) Complexes: Reactivity Scope, Mechanism, and Computations},
author = {Zhang, Shaoguang and Li, Haixia and Appel, Aaron M. and Hall, Michael B. and Bullock, R. Morris},
abstractNote = {The synthesis of heteroleptic [Ni(P2N2)(diphosphine)][BF4]2 complexes and the cleavage of P–C and C–H bonds of the P2N2 ligand in those complexes are reported here. The products are five-coordinate complexes in which Ni–C and P–H bonds have formed to give a cyclic moiety containing Ni–CH$=$NR2. The reactivity of [Ni(P2N2)(diphosphine)][BF4]2 complexes is influenced by the rigidity of the diphosphine, the steric effect of the substituents, and length of the carbon linker of the diphosphine ligands. Diphosphine ligands bearing a rigid backbone (e.g., dmpbz, 1,2-bis(dimethylphosphino)benzene) or aromatic substituents (e.g., dppe, 1,2-bis(diphenylphosphino)ethane) react with [Ni(PtBu2NBn2)(CH3CN)2][BF4]2 to give P–C/C–H bond cleavage products. Both [Ni(PtBu2NBn2)(dmpe)(MeCN)][BF4]2 and [Ni(PtBu2NBn2)(dmpm)(MeCN)][BF4]2 (dmpm = 1,2-bis(dimethylylphosphino)methane) were prepared by the reaction of [Ni(PtBu2NBn2)(CH3CN)2][BF4]2 with the corresponding diphosphine ligands. [Ni(PtBu2NBn2)(dmpe)(MeCN)][BF4]2 readily undergoes P–C/C–H bond cleavage in nitromethane. In sharp contrast, [Ni(PtBu2NBn2)(dmpm)][BF4]2 is stabilized by dmpm, a diphosphine with small bite angle, and does not show P–C/C–H bond cleavage reactivity. Computational results show that for complexes bearing less bulky diphosphine ligands, such as dmpm, the barriers for the rate-determining transition states are in some examples higher than 30 kcal/mol with the M06 functional, higher than those for complexes bearing more rigid or more bulky ligands, consistent with experimental studies. The calculated barriers for the first transition state correlated with increased values of the dihedral angle formed by the two NiP2 planes.},
doi = {10.1021/acs.organomet.0c00388},
journal = {Organometallics},
number = 18,
volume = 39,
place = {United States},
year = {Thu Sep 03 00:00:00 EDT 2020},
month = {Thu Sep 03 00:00:00 EDT 2020}
}
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