Details of Grant 

EPSRC Reference:	EP/F037465/1
Title:	Diphosphatetrylenes: advances in the chemistry of heavier group 14 carbene analogues
Principal Investigator:	Izod, Dr K
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department:	School of Chemistry
Organisation:	Newcastle University
Scheme:	Standard Research
Starts:	02 June 2008	Ends:	01 June 2011	Value (£):	318,410
EPSRC Research Topic Classifications:	Chemical Synthetic Methodology
EPSRC Industrial Sector Classifications:	Chemicals
Related Grants:
Panel History:	Panel Date Panel Name Outcome 27 Nov 2007 Chemistry Prioritisation Panel (Science) Announced
Summary on Grant Application Form
The isolation of stable low-coordination number and low oxidation state derivatives of the group 14 elements (i.e. formal analogues of carbenes, alkenes, alkynes and related species) remains one of the most exciting and challenging areas of contemporary main group chemistry. Within this field the isolation of heavier carbene analogues holds a special fascination as, in addition to fundamental questions regarding their structures and bonding, these compounds may also act as ligands to transition and other metal centres. Although the chemistry of stable diaminocarbenes and their silicon analogues has emerged only recently, the corresponding heavier diaminotetrylenes (R2N)2E [E = Ge, Sn, Pb] have been known since the 1970s. The electron-deficient, low oxidation state group 14 centres in these compounds are stabilised by donation of electron density from the niotrogen lone pairs into the vacant p orbital at the group 14 centre. It is notable that, in contrast to the diaminotetrylenes, analogous compounds with phosphorus (the element directly below nitrogen in the periodic table) adjacent to a divalent group 14 atom are virtually unknown. This is, in part, due to the perception that lone pair donation from phosphorus to an adjacent electron-deficient centre would be poor. However, recent calculations suggest that this is not the case and our own preliminary experiments suggest that a wide range of such compounds is readily accessible.This proposal seeks to build on our preliminary results through the synthesis of an extensive array of phosphorus-substituted, divalent group 14 compounds (phosphatetrylenes) and the study of their structures, bonding and reactions. In the course of these studies we will investigate the donor/acceptor properties of our compounds when bound to transition metals. One of the potential drawbacks of current diaminocarbene chemistry is the limited nature of the changes that may be made to the donor/acceptor properties of these compounds. In contrast, the substituents at phosphorus in our compounds may be readily modified and so the donor/acceptor properties may be altered, permitting the synthesis of phosphatetrylenes having a wide range of properties. These ligands thus have the potential to complement diaminocarbene ligands in transition metal-based catalysts, providing an effective mechanism to tune catalyst properties.
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