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Unprecedented η3-Coordination and Functionalization of the 2-Phosphaethynthiolate Anion at Lanthanum(III)

preprint
submitted on 13.01.2021, 10:31 and posted on 13.01.2021, 13:44 by Fabian A. Watt, Lukas Burkhardt, Roland Schoch, Stefan Mitzinger, Matthias Bauer, Florian Weigend, Jose M. Goicoechea, Frank Tambornino, Stephan Hohloch
We present the unprecedented η3-coordination of the 2-phosphaethynthiolate anion in the complex (PN)2La(SCP) (2) [PN = N-(2-(diisopropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide)]. Structural comparison with dinuclear thiocyanate bridged (PN)2La(μ-1,3-SCN)2La(PN)2 (3) and azide bridged (PN)2La(μ-1,3-N3)2La(PN)2 (4) complexes indicates that the [SCP] coordination mode is mainly governed by electronic, rather than steric factors. Quantum mechanical investigations reveal large contributions of the antibonding π-orbital of the [SCP] ligand to the LUMO of complex 2, rendering it the ideal precursor for the first functionalization of the [SCP] anion. Complex 2 was therefore reacted with CAACs which induced a selective rearrangement of the [SCP] ligand to form the first CAAC stabilized group 15 – group 16 fulminate-type complexes (PN)2La{SPC(RCAAC)} (5a,b) (R = Ad, Me). A detailed reaction mechanism for the SCP to SPC isomerization is proposed based on DFT calculations.

Funding

DFG TA 1357/1-1

DFG MI 2561/1-1

Daimler and Benz Foundation

Fonds der chemischen Industrie

University of Paderborn

University of Innsbruck

DFG BA 4467/6-1

History

Email Address of Submitting Author

Stephan.Hohloch@uibk.ac.at

Institution

University of Innsbruck

Country

Austria

ORCID For Submitting Author

0000-0002-5353-0801

Declaration of Conflict of Interest

The authors declare no Conflict of Interest.

Version Notes

Orignal Version

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