1,4-Addition of a Terminal Phosphinidene Complex to [5]Metacyclophane

Maurice J van Eis; Corine M D Komen; Franciscus J J de Kanter; Willem H de Wolf; Koop Lammertsma; Friedrich Bickelhaupt; Martin Lutz; Anthony L Spek

doi:10.1002/(SICI)1521-3773(19980619)37:11<1547::AID-ANIE1547>3.0.CO;2-S

1,4-Addition of a Terminal Phosphinidene Complex to [5]Metacyclophane

Angew Chem Int Ed Engl. 1998 Jun 19;37(11):1547-1550. doi: 10.1002/(SICI)1521-3773(19980619)37:11<1547::AID-ANIE1547>3.0.CO;2-S.

Authors

Maurice J van Eis¹, Corine M D Komen¹, Franciscus J J de Kanter¹, Willem H de Wolf¹, Koop Lammertsma¹, Friedrich Bickelhaupt¹, Martin Lutz², Anthony L Spek²

Affiliations

¹ Scheikundig Laboratorium, Vrije Universiteit, De Boelelaan 1083, NL-1081 HV Amsterdam (The Netherlands), Fax. (+31) 20-4447488.
² Bijvoet Center for Biomolecular Research, Department of Crystal and Structural Chemistry, Utrecht University (The Netherlands).

Abstract

Three novel aspects emerge for the reaction of [5]metacyclophane (1) with the (intermediate) phenylphosphinidene complex 2 to give the 7-phosphanorbornadiene 3. It is the first 1,4-addition of a phosphinidene complex to an unsaturated system, the first addition of a phosphinidene complex to a benzene ring, and the first [4+1] cycloaddition to an aromatic compound.

Keywords: Cycloadditions; Cyclophanes; Density functional calculations; Phosphinidene complexes; Phosphorus.