Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds
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nihms-1654395.pdf
Description
Accepted version
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1.43 MB
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Author(s)
Hwang, Seung Jun
Tanushi, Akira
Radosevich, Alexander T.
Date Issued
December 2020
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Hwang, Seung Jun, Tanushi, Akira and Radosevich, Alexander T. 2020. "Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds." Journal of the American Chemical Society, 142 (51).
Version
Author's final manuscript
Abstract
© Insertion of a tricoordinate phosphorus ligand into late metal-carbon bonds is reported. Metalation of a P^P-chelating ligand (L1), composed of a nontrigonal phosphorous (i.e., P(III)) triamide moiety, P(N(o-N(Ar)C6H4)2, tethered by a phenylene linker to a -PiPr2 anchor, with group 10 complexes L2M(Me)Cl (M = Ni, Pd) results in insertion of the nontrigonal phosphorus site into the metal-methyl bond. The stable methylmetallophosphorane compounds thus formed are characterized spectroscopically and crystallographically. Metalation of L1 with (cod)PtII(Me)(Cl) does not lead to a metallophosphorane but rather to the standard bisphosphine chelate (κ2-L1)Pt(Me)(Cl). These divergent reactivities within group 10 are rationalized by reference to periodic variation in M-C bond enthalpies.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/jacs.0c11161
