Diastereoselective Template Synthesis on Iron and Uranium

Carpenter, Stephanie H.; Billow, Brennan S.; Tondreau, Aaron M.

doi:10.1021/acs.organomet.1c00296

Diastereoselective Template Synthesis on Iron and Uranium

Journal Article · Fri Jul 09 00:00:00 EDT 2021 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.1c00296· OSTI ID:1812669

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Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

The addition of 2 equiv of ^tBu₂PSiMe₃ to 2,6-pyridinedicarboxaldehyde ((CHO)₂Py) results in a rac/meso diastereomeric mixture of the PNP-chelating ligand 2,6-bis((trimethylsiloxy)(di-tert-butylphosphino)-methyl)-pyridine (^(OTMS)PNP^tBu) (1-r/m) via addition of the P–Si bond across both of the aldehyde C–O bonds. Chelation of ^(OTMS)PNP^tBu to FeCl₂ results in the same diastereotopic ratio of (^(OTMS)PNP^tBu)FeCl₂ (2-r/m) as the free ligand. Fractional crystallization allows for the isolation of the C₂ isomer, 2-r, and a template synthesis protocol allows for the synthesis and isolation of the C_s isomer, 2-m, in good yield. Furthermore, the template synthesis protocol was also expanded to the f-block with the use of UCl₄ in order to assess the specificity of the template synthesis on a larger metal cation. This reaction performed on UCl₄ forms the meso diastereospecific uranium complex (^(tBu2P)ONO)UCl₂(dtbpy), 3-m, with observation of the rational intermediate (^(OTMS)PNO^tBu)UCl₃(dtbpy), 4-m, which arose from the respective formation of two- or one-equivalents of TMS–Cl and formation of the corresponding U–O bond.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1812669

Report Number(s):: LA-UR-21-20777

Journal Information:: Organometallics, Vol. 40, Issue 15; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Diastereoselective Template Synthesis on Iron and Uranium

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