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η 3 ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III) **
Author(s) -
Watt Fabian A.,
Burkhardt Lukas,
Schoch Roland,
Mitzinger Stefan,
Bauer Matthias,
Weigend Florian,
Goicoechea Jose M.,
Tambornino Frank,
Hohloch Stephan
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202100559
Subject(s) - chemistry , steric effects , thiocyanate , isomerization , ligand (biochemistry) , azide , stereochemistry , ion , coordination complex , crystallography , surface modification , inorganic chemistry , organic chemistry , metal , receptor , biochemistry , catalysis
We present the η 3 ‐coordination of the 2‐phosphaethynthiolate anion in the complex (PN) 2 La(SCP) ( 2 ) [PN=N‐(2‐(diisopropylphosphanyl)‐4‐methylphenyl)‐2,4,6‐trimethylanilide)]. Structural comparison with dinuclear thiocyanate‐bridged (PN) 2 La(μ‐1,3‐SCN) 2 La(PN) 2 ( 3 ) and azide‐bridged (PN) 2 La(μ‐1,3‐N 3 ) 2 La(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) 2 La{SPC( R CAAC)} ( 5 a,b , R=Ad, Me). A detailed reaction mechanism for the SCP‐to‐SPC isomerization is proposed based on DFT calculations.