Preparation of U(IV) kappa(1)-amidinate complexes by nitrile metathesis

Treating U(IV) imido compounds, Tp*U-2(N-p-methoxyphenyl) (2-OMe) and Tp*U-2(N-pTol) (2-pTol), with benzonitrile or 4-cyanopyridine results in unusual products of multiple bond metathesis ([2 pi+2 pi]-cycloaddition and [2 pi+2 pi]-cycloreversion). H-1 and B-11 NMR, infrared, and electronic absorptio...

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Bibliographic Details
Published inPolyhedron Vol. 158; pp. 1 - 7
Main Authors Tatebe, Caleb J., Collins, Tyler S., Barnett, Grant Reed, Zeller, Matthias, Bart, Suzanne C.
Format Journal Article
LanguageEnglish
Published OXFORD Elsevier 15.01.2019
Subjects
Chemistry
Chemistry, Inorganic & Nuclear
Crystallography
Physical Sciences
Science & Technology
Cycloaddition
ACTIVATION
Uranium
AZIDES
TERMINAL-IMIDO METALLOCENE
Scorpionate ligands
REACTIVITY
Actinide chemistry
COORDINATION
LIGAND
CARBON-DIOXIDE
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Summary:Treating U(IV) imido compounds, Tp*U-2(N-p-methoxyphenyl) (2-OMe) and Tp*U-2(N-pTol) (2-pTol), with benzonitrile or 4-cyanopyridine results in unusual products of multiple bond metathesis ([2 pi+2 pi]-cycloaddition and [2 pi+2 pi]-cycloreversion). H-1 and B-11 NMR, infrared, and electronic absorption spectroscopic analyses provides evidence of tetravalent uranium compounds, while X-ray crystallography confirmed molecular structures to be Tp*U-2[=N-C(=N-pOMePh)pyr] (3-py), Tp*U-2[=N-C(=N-pOMePh)Ph] (3-Ph), Tp*U-2[=N-C(=N-pTol)pyr] (4-py), Tp*U-2[=N-C(=N-pTol)Ph] (4-Ph), Tp*U-2[=N-C(=N-pOMePh)p-CNPh] (5-OMe), and Tp*U-2[=N-C(=N-pTol)p-CNPh] (5-Tol). Previous examples of actinide imidos treated with nitriles resulted in cyclometallated products; thus, the compounds reported represent divergent chemistry in that an kappa(1)-amidinate ligand is formed through [2 pi+2 pi]-cycloaddition and [2 pi+2 pi]-cycloreversion. (C) 2018 Elsevier Ltd. All rights reserved.
ISSN:0277-5387
DOI:10.1016/j.poly.2018.10.042