Open AccessMetalate‐Mediated Functionalization of P 4 by Trapping Anionic [Cp*Fe(CO) 2 (η 1 ‐P 4 )] − with Lewis Acids
Author(s) -
Borger Jaap E.,
Jongkind Maarten K.,
Ehlers Andreas W.,
Lutz Martin,
Slootweg J. Chris,
Lammertsma Koop
Publication year - 2017
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.201700027
Subject(s) - chemistry , surface modification , protonation , lewis acids and bases , reactivity (psychology) , white phosphorus , transition metal , catalysis , nucleophile , medicinal chemistry , stereochemistry , ion , phosphorus , organic chemistry , medicine , alternative medicine , pathology
The development of selective functionalization strategies of white phosphorus (P 4 ) is important to avoid the current chlorinated intermediates. The use of transition metals (TMs) could lead to catalytic procedures, but these are severely hampered by the high reactivity and unpredictable nature of the tetrahedron. Herein, we report selective first steps by reacting P 4 with a metal anion [Cp*Fe(CO) 2 ] − (Cp*=C 5 (CH 3 ) 5 ), which, in the presence of bulky Lewis acids (LA; B(C 6 F 5 ) 3 or BPh 3 ), leads to unique TM‐substituted LA‐stabilized bicyclo[1.1.0]tetraphosphabutanide anions [Cp*Fe(CO) 2 (η 1 ‐P 4 ⋅LA)] − . Their P‐nucleophilic site can be subsequently protonated to afford the transient LA‐free neutral butterflies exo , endo ‐ and exo , exo ‐Cp*Fe‐ (CO) 2 (η 1 ‐P 4 H), allowing controllable stepwise metalate‐mediated functionalization of P 4 .