article published Fabian A. Watt author Lukas Burkhardt author Roland Schoch author 484670000-0003-2061-7289 Stefan Mitzinger author Matthias Bauer author 472410000-0002-9294-6076 Florian Weigend author Jose M. Goicoechea author Frank Tambornino author Stephan Hohloch author 35 department 306 department 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. Wiley2021 eng General ChemistryCatalysis 1433-7851 1521-377310.1002/anie.202100559 60179534-9539 Watt, F. A., Burkhardt, L., Schoch, R., Mitzinger, S., Bauer, M., Weigend, F., Goicoechea, J. M., Tambornino, F., &#38; Hohloch, S. (2021). η            ³            ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**. <i>Angewandte Chemie International Edition</i>, <i>60</i>(17), 9534–9539. <a href="https://doi.org/10.1002/anie.202100559">https://doi.org/10.1002/anie.202100559</a> 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. @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={<a href="https://doi.org/10.1002/anie.202100559">10.1002/anie.202100559</a>}, 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., et al. “η            ³            ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**.” <i>Angewandte Chemie International Edition</i>, vol. 60, no. 17, Wiley, 2021, pp. 9534–39, doi:<a href="https://doi.org/10.1002/anie.202100559">10.1002/anie.202100559</a>. Watt FA, Burkhardt L, Schoch R, et al. η            ³            ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**. <i>Angewandte Chemie International Edition</i>. 2021;60(17):9534-9539. doi:<a href="https://doi.org/10.1002/anie.202100559">10.1002/anie.202100559</a> F. A. Watt <i>et al.</i>, “η            ³            ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**,” <i>Angewandte Chemie International Edition</i>, vol. 60, no. 17, pp. 9534–9539, 2021, doi: <a href="https://doi.org/10.1002/anie.202100559">10.1002/anie.202100559</a>. 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)**.” <i>Angewandte Chemie International Edition</i> 60, no. 17 (2021): 9534–39. <a href="https://doi.org/10.1002/anie.202100559">https://doi.org/10.1002/anie.202100559</a>. 410102023-01-30T17:00:21Z2023-01-31T08:06:50Z