Cu(I) complexes with a noninnocent PNP ligand: selective dearomatization and electrophilic addition reactivity.
The neutral, T-shaped complex Cu(I)(PN(-)P(tBu)) (2), featuring a dearomatized 2,6-bis(diphosphino)pyridine (PNP)-pincer ligand, is shown to interact rapidly with electrophiles. This has enabled the synthesis of acetato complex 3. Furthermore, C-C bond formation onto the deprotonated methylene-bridgehead carbon is observed with MeOTf as the electrophile. This represents the first case of selective modification of the lutidine-based backbone of such noninnocent PNP ligands. Theoretical calculations support the formation of monomeric complex 2 and indicate the high reactivity of the methylene fragment in this Cu(I) complex.
van der Vlugt
Jarl Ivar
JI
Supramolecular & Homogeneous Catalysis Group, van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands. j.i.vandervlugt@uva.nl
Pidko
Evgeny A
EA
Vogt
Dieter
D
Lutz
Martin
M
Spek
Anthony L
AL