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Phosphine Carboxylate—Probing the Edge of Stability of a Carbon Dioxide Adduct with Dihydrogenphosphide
Author(s) -
Schreiber Roy E.,
Goicoechea Jose M.
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202013914
Subject(s) - chemistry , carboxylate , phosphine , electrophile , protonation , decarboxylation , reactivity (psychology) , substituent , surface modification , adduct , hydrolysis , organic chemistry , carbon dioxide , medicinal chemistry , inorganic chemistry , photochemistry , ion , catalysis , medicine , alternative medicine , pathology
We present a new adduct of carbon dioxide with dihydrogenphosphide, that may be prepared either by direct reaction of NaPH 2 with carbon dioxide or by hydrolysis of the phosphaethynolate ion (PCO − ). In this hydrolysis transformation, a new mechanism is proposed for the electrophilic reactivity of the phosphaethynolate ion. Protonation to form phosphine carboxylic acid (PH 2 COOH) and functionalization to form esters is shown to increase the strength of the P–C interaction, allowing for comparisons to be drawn between this species and the analogous carbamic (NH 2 COOH) and carbonic acids (H 2 CO 3 ). Functionalization of the oxygen atom is found to stabilize the phosphine carboxylate while also allowing solubility in organic solvents whereas phosphorus functionalization is shown to facilitate decarboxylation. Substituent migration occurs in some cases.