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Structural Snapshots in Reversible Phosphinidene Transfer: Synthetic, Structural, and Reaction Chemistry of a Sn═P Double Bond.

ABSTRACT: The reaction of amido-substituted stannylenes with phospha-Wittig reagents (Me₃PPR) results in release of hexamethyldisilazane and tethering of the resulting -CH₂PMe₂PR fragment to the tin center to give P-donor stabilized stannylenes featuring four-membered Sn,C,P,P heterocycles. Through systematic increases in steric loading, the structures of these systems in the solid state can be tuned, leading to successive P-P bond lengthening and Sn-P contraction and, in the most encumbered case, to complete P-to-Sn transfer of the phosphinidene fragment. The resulting stannaphosphene features a polar Sn═P double bond as determined by structural and computational studies. The reversibility of phosphinidene transfer can be established by solution phase measurements and reactivity studies.

SUBMITTER: Fischer M

PROVIDER: S-EPMC9136930 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature

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Structural Snapshots in Reversible Phosphinidene Transfer: Synthetic, Structural, and Reaction Chemistry of a Sn═P Double Bond.

Fischer Malte M Roy Matthew M D MMD Wales Lewis L LL Ellwanger Mathias A MA Heilmann Andreas A Aldridge Simon S

Journal of the American Chemical Society 20220510 20

The reaction of amido-substituted stannylenes with phospha-Wittig reagents (Me3PPR) results in release of hexamethyldisilazane and tethering of the resulting -CH2PMe2PR fragment to the tin center to give P-donor stabilized stannylenes featuring four-membered Sn,C,P,P heterocycles. Through systematic increases in steric loading, the structures of these systems in the solid state can be tuned, leading to successive P-P bond lengthening a ...[more]

PMID: 35536684

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