η 3 ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**
F.A. Watt, L. Burkhardt, R. Schoch, S. Mitzinger, M. Bauer, F. Weigend, J.M. Goicoechea, F. Tambornino, S. Hohloch, Angewandte Chemie International Edition 60 (2021) 9534–9539.
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Author
Watt, Fabian A.;
Burkhardt, Lukas;
Schoch, RolandLibreCat 
;
Mitzinger, Stefan;
Bauer, MatthiasLibreCat ;
Weigend, Florian;
Goicoechea, Jose M.;
Tambornino, Frank;
Hohloch, Stephan
;
Mitzinger, Stefan;
Bauer, MatthiasLibreCat ;
Weigend, Florian;
Goicoechea, Jose M.;
Tambornino, Frank;
Hohloch, StephanAbstract
We present the 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)} (5 a,b, R=Ad, Me). A detailed reaction mechanism for the SCP-to-SPC isomerization is proposed based on DFT calculations.
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Journal Title
Angewandte Chemie International Edition
Volume
60
Issue
17
Page
9534-9539
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Watt FA, Burkhardt L, Schoch R, et al. η 3 ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**. Angewandte Chemie International Edition. 2021;60(17):9534-9539. doi:10.1002/anie.202100559
Watt, F. A., Burkhardt, L., Schoch, R., Mitzinger, S., Bauer, M., Weigend, F., Goicoechea, J. M., Tambornino, F., & Hohloch, S. (2021). η 3 ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**. Angewandte Chemie International Edition, 60(17), 9534–9539. https://doi.org/10.1002/anie.202100559
@article{Watt_Burkhardt_Schoch_Mitzinger_Bauer_Weigend_Goicoechea_Tambornino_Hohloch_2021, title={η 3 ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**}, volume={60}, DOI={10.1002/anie.202100559}, number={17}, journal={Angewandte Chemie International Edition}, publisher={Wiley}, author={Watt, Fabian A. and Burkhardt, Lukas and Schoch, Roland and Mitzinger, Stefan and Bauer, Matthias and Weigend, Florian and Goicoechea, Jose M. and Tambornino, Frank and Hohloch, Stephan}, year={2021}, pages={9534–9539} }
Watt, Fabian A., Lukas Burkhardt, Roland Schoch, Stefan Mitzinger, Matthias Bauer, Florian Weigend, Jose M. Goicoechea, Frank Tambornino, and Stephan Hohloch. “η 3 ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**.” Angewandte Chemie International Edition 60, no. 17 (2021): 9534–39. https://doi.org/10.1002/anie.202100559.
F. A. Watt et al., “η 3 ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**,” Angewandte Chemie International Edition, vol. 60, no. 17, pp. 9534–9539, 2021, doi: 10.1002/anie.202100559.
Watt, Fabian A., et al. “η 3 ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**.” Angewandte Chemie International Edition, vol. 60, no. 17, Wiley, 2021, pp. 9534–39, doi:10.1002/anie.202100559.
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