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Department of Chemistry

Publication details for Dr Dominikus Heift

Heift, D., Benkő, Z. & Grützmacher, H. (2014). Is the phosphaethynolate anion, (OCP)-, an ambident nucleophile? A spectroscopic and computational study. Dalton Transactions 43(15): 5920-5928.

Author(s) from Durham

Abstract

The reactivity of Na(OCP) was investigated towards triorganyl compounds of the heavier group 14 elements (R3EX R = Ph or iPr; E = Si, Ge, Sn, Pb; X = Cl, OTf). In the case of E = Si two constitutional isomers were formed and characterised in situ: R3Si–O–C[triple bond, length as m-dash]P is the kinetic and R3Si–P[double bond, length as m-dash]C[double bond, length as m-dash]O is the thermodynamic product, representing experimental evidence of the ambident character of the (OCP)− anion. Applying theoretical calculations and spectroscopic methods, the compound previously reported as iPr3Si–O–C[triple bond, length as m-dash]P can now unambiguously be identified as iPr3Si–P[double bond, length as m-dash]C[double bond, length as m-dash]O. The heavier analogues form exclusively the phosphaketene isomer R3E–P[double bond, length as m-dash]C[double bond, length as m-dash]O (E = Ge, Sn, Pb). DFT calculations were performed to gain deeper insight into the bonding and thermodynamic stability of these compounds.