η ³ ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)** Watt, Fabian A. Burkhardt, Lukas Schoch, Roland Mitzinger, Stefan Bauer, Matthias Weigend, Florian Goicoechea, Jose M. Tambornino, Frank Hohloch, Stephan General Chemistry Catalysis 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. Wiley 2021 info:eu-repo/semantics/article doc-type:article text http://purl.org/coar/resource_type/c_6501 https://ris.uni-paderborn.de/record/41010 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> eng info:eu-repo/semantics/altIdentifier/doi/10.1002/anie.202100559 info:eu-repo/semantics/altIdentifier/issn/1433-7851 info:eu-repo/semantics/altIdentifier/issn/1521-3773 info:eu-repo/semantics/closedAccess