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A Stable Primary Phosphane Oxide and Its Heavier Congeners
Author(s) -
Horký Filip,
Císařová Ivana,
Štěpnička Petr
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202003702
Subject(s) - chemistry , steric effects , medicinal chemistry , tautomer , oxide , sulfur , chalcogen , selenide , sulfide , pnictogen , hydrogen peroxide , stereochemistry , organic chemistry , selenium , physics , superconductivity , quantum mechanics
(Ferrocenylmethyl)phosphane ( 1 ) oxidation with hydrogen peroxide, elemental sulfur and grey selenium produced (ferrocenylmethyl)phosphane oxide 1O , sulfide 1S and selenide 1Se , respectively, as the first isolable primary phosphane chalcogenides lacking steric protection. At elevated temperatures, compound 1O disproportionated into 1 and (ferrocenylmethyl)phosphinic acid. In reactions with [(η 6 ‐mes)RuCl 2 ] 2 , 1O underwent tautomerization into a phosphane complex [(η 6 ‐mes)RuCl 2 {FcCH 2 PH(OH)‐ κP }], whereas 1S and 1Se lost their P‐bound chalcogen atoms, giving rise to the phosphane complex [(η 6 ‐mes)RuCl 2 (FcCH 2 PH 2 ‐ κP )] (Fc=ferrocenyl, mes=mesitylene). No tautomerization was observed in the reaction of 1O with B(C 6 F 5 ) 3 , which instead produced a Lewis pair FcCH 2 P(O)H 2 ‐B(C 6 F 5 ) 3 . Phosphane oxide 1O added to C=O bonds of aldehydes and ketones and even to cumulenes PhNCE (E=O and S). However, both PH hydrogens were only employed in the reactions with aldehydes and cyanates.