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Solid/Gas In Crystallo Reactivity of an Ir(I) Methylidene Complex

Altus, Kristof M.; Sajjad, M. Arif; Gyton, Matthew R.; Whitwood, Adrian C.; Page, Samuel J.; Macgregor, Stuart A.; Weller, Andrew S.

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Kristof M. Altus

M. Arif Sajjad

Matthew R. Gyton

Adrian C. Whitwood

Dr Samuel Page
Manager Solid-State NMR Research Service

Stuart A. Macgregor

Andrew S. Weller


In crystallo stabilization of known, but solution unstable, methylidene complex [Ir(tBu-PONOP)(═CH2)][BArF4] allows single-crystal to single-crystal solid/gas reactivity associated with the {Ir═CH2} group to be studied. Addition of H2 results in [Ir(tBu-PONOP)(H)2][BArF4]; exposure to CO forms iridium(I) carbonyl [Ir(tBu-PONOP)(CO)][BArF4], and reaction with NH3 gas results in the formation of methylamine complex [(tBu-PONOP)Ir(NH2Me)][BArF4] via an aminocarbene intermediate. Periodic density functional theory and electronic structure analyses confirm the Ir═CH2 bond character but with a very low barrier to rotation around the Ir═CH2 bond. Calculations show that addition of NH3 to the electrophilic alkylidene carbon gives an initial ammonium ylid intermediate. Stepwise N–H and C–H transfers then form the aminocarbene intermediate as a kinetic product from which two successive C–H couplings lead to the more stable methylamine product.


Altus, K. M., Sajjad, M. A., Gyton, M. R., Whitwood, A. C., Page, S. J., Macgregor, S. A., & Weller, A. S. (2024). Solid/Gas In Crystallo Reactivity of an Ir(I) Methylidene Complex. Organometallics,

Journal Article Type Article
Acceptance Date Mar 26, 2024
Online Publication Date Jun 6, 2024
Publication Date Jun 6, 2024
Deposit Date Jul 1, 2024
Publicly Available Date Jul 1, 2024
Journal Organometallics
Print ISSN 0276-7333
Electronic ISSN 1520-6041
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Public URL


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