Is the phosphaethynolate anion, (OCP)-, an ambident nucleophile? A spectroscopic and computational study.

Heift, D.; Benkő, Z.; Grützmacher, H.

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.

Citation

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. https://doi.org/10.1039/c3dt53569j

• Journal Article Type: Article
• Acceptance Date: Jan 30, 2014
• Online Publication Date: Jan 30, 2014
• Publication Date: 2014-04
• Deposit Date: Feb 21, 2017
• Journal: Dalton Transactions
• Print ISSN: 1477-9226
• Electronic ISSN: 1477-9234
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 43
• Issue: 15
• Pages: 5920-5928
• DOI: https://doi.org/10.1039/c3dt53569j
• Public URL: https://durham-repository.worktribe.com/output/1385448