The concept of frustrated Lewis pairs (FLPs) is now well established, in which the unquenched reactivity of main group Lewis acid/base pairs shows remarkable facility towards small molecule activation, such as reversible heterolytic H2 splitting.1,2 The Wass group3 and others4 expanded the scope of Lewis acids in FLPs to group 4 transition metals, demonstrated that this is a useful concept beyond the main group. The parent phosphane zirconocene complexes I mimic main group FLP-type reactivity but also demonstrated novel FLP reaction modes which have not yet been observed for main group systems. Figure 1. <img src='https://acs-archive-assets2.s3.amazonaws.com/241nm/uploads/74111_figure1.jpg' alt='' />This paper will describe our recent studies to understand and extend early transition metal FLPs, inspired by the zirconocene-phosphane complex I . Area of particular focus are: a) exchanging the 'soft' phosphane moiety for a 'harder' nitrogen Lewis base (see II ); b) the diversification of the aromatic scaffold which links the Lewis base to the electrophilic transition metal fragment (III ); c) the exchange of the cationic group 4 fragment by an isolobal and isoelectric neutral group 3 moiety (IV ).1Science 2006 , 314, 1124; Dalton Trans. 2007 , 3407.2Angew. Chem., Int. Ed. 2010 , 49, 46.3 J. Am. Chem. Soc. 2011 , 133, 8826; J. Am. Chem. Soc. 2011 , 133, 18463; Eur. J. Inorg. Chem. 2012 , 1546; Dalton Trans. 2012 , 41, 9067.4Chem. Sci. 2011 , 2, 170; Chem. Commun. 2012 , 48, 6109; J. Am. Chem. Soc. 2013 , 135, 6465; Organometallics 2013 , 32, 7306; Angew. Chem. Int. Ed. 2013 , 52, 13629.

Frustrated Lewis pairs based on early transition metals

248th National Meeting (2014)

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