4.7 Article

Martin's Phosphino-Triol Revisited: Unexpected P-C Bond Cleavage Reactions and Their Suppression via Complexation of Al3+ and Sc3+

Journal

INORGANIC CHEMISTRY
Volume 60, Issue 24, Pages 19414-19420

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c03232

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Funding

  1. state of BadenWurttemberg through bwHPC
  2. German Research Foundation (DFG)

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A revised synthesis of Martin's phosphino-triols was reported, demonstrating their selective disassembly through an unexpected P-C bond cleavage reaction. This degradation pathway was effectively suppressed by complexation of Al3+ and Sc3+. The resulting half-cage complexes exhibited a unique kappa(4)-P,O,O',O ''-coordination mode not seen in other phosphino-triols.
A revised synthesis of Martin's phosphino-triols (two derivatives) is reported. Once isolated, these thermally sensitive triols were shown to disassemble selectively via an unexpected P-C bond cleavage reaction. This degradation pathway was effectively suppressed via complexation of Al3+ and Sc3+. In the resulting half-cage complexes, the ligand scaffold is bound to each metal (Al(3+ )and Sc3+, respectively) via all four donor atoms. So far, this kappa(4)-P,O,O',O ''-coordination mode has not been observed for any other phosphino-triol.

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