Are monophospha(III)amidines and -guanidines with ionizable hydrogens tautomeric? Towards a deeper understanding of two related hetero-element functional groups

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dc.contributor.authorMasuda, Jason D.
dc.contributor.authorAmrei, Leila M.
dc.contributor.authorBoeré, René T.
dc.date.accessioned2024-06-21T19:55:04Z
dc.date.available2024-06-21T19:55:04Z
dc.date.issued2023
dc.descriptionOpen access article. Creative Commons Attribution 4.0 International Deed license (CC BY 4.0) applies
dc.description.abstractThis paper presents definitive structural evidence for N,P(III)-monophosphaamidines in P=C and N=C isomeric forms from a combination of new syntheses, single-crystal X-ray diffraction (SC-XRD), solid-state NMR and FTIR. Evidence is also provided for C-amino-(σ2,λ3)-phosphaalkene and C-(σ3,λ3)-phosphinoimine tautomerism in solution using multi-nuclear NMR methods. Synthesis and SC-XRD structure determination of a trisubstituted N,N’,P(III)-monophosphaguanidine is presented, the first structure of a phospha(III)guanidine with two ionizable H atoms. The structural evidence is convincing for an N=C geometry, resulting in both N−H and P−H in the molecule. A detailed computational investigation using DFT methods is presented, with the goal of understanding the tautomeric structure preferences both at the fundamental level (parent molecules with all substituents on the heteroatoms being hydrogen) and using the full structures containing the very bulky 2,6-diisopropylphenyl (Dipp) substituents employed in this study. Arguments are espoused for treating phospha(III)amidines and -guanidines as new types of functional groups, similar to but distinct from the familiar organic analogues. Limited reactivity studies and a voltammetry study of one phospha(III)amidine are included with the supporting information.
dc.description.peer-reviewYes
dc.identifier.citationMasuda, J. D., Amrei, L. M., & Boeré, R. T. (2023). Are monophospha(III)amidines and -guanidines with ionizable hydrogens tautomeric? Towards a deeper understanding of two related hetero-element functional groups. European Journal of Inorganic Chemistry, 26, Article e202300495. https://doi.org/10.1002/ejic.202300495
dc.identifier.urihttps://hdl.handle.net/10133/6798
dc.language.isoen
dc.publisherWiley
dc.publisher.departmentDepartment of Chemistry and Biochemistry
dc.publisher.facultyArts and Science
dc.publisher.institutionSaint Mary's University
dc.publisher.institutionUniversity of Lethbridge
dc.publisher.urlhttps://doi.org/10.1002/ejic.202300495
dc.subjectAminophosphaalkenes
dc.subjectComputational chemistry
dc.subjectIsomerism
dc.subjectPhosphinoimine
dc.subjectHirshfeld atom refinement
dc.titleAre monophospha(III)amidines and -guanidines with ionizable hydrogens tautomeric? Towards a deeper understanding of two related hetero-element functional groups
dc.typeArticle
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