B‑Centered Reactivity of Persistent P‑Stabilized Boryl Radicals
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https://figshare.com/articles/dataset/B_Centered_Reactivity_of_Persistent_P_Stabilized_Boryl_Radicals/5394949
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资源简介：
A new P-stabilized
boryl radical [iPr2P(naph)BMes]• 2a was obtained by reduction
of the corresponding phosphino-bromoborane 1a with Na(Hg).
The persistent radical 2a has been characterized by EPR,
and its structure has been thoroughly studied by DFT. The corresponding
Gomberg-type dimer has been analyzed by NMR and XRD, and the Gibbs
free energy associated with the dimerization process has been evaluated
by VT EPR. The replacement of the Ph substituents at phosphorus for iPr groups has a slight but noticeable impact: it increases
the spin density at boron and favors the radical over its Gomberg-type
dimer. An original cross-coupling product between 2a and
the trityl radical Ph3C• has also been
authenticated crystallographically. The P-stabilized boryl radicals 2a,b are readily trapped by TEMPO to give the corresponding
B–O adducts 3a,b (naphthyl-bridged phosphine-boranes
without P → B interaction). The reaction of 2a,b with Ph3CCl substantiates their ability to participate
in halogen transfer reactions.
创建时间：
2017-09-11
