Fabian A Watt1, Lukas Burkhardt1, Roland Schoch1, Stefan Mitzinger2, Matthias Bauer1, Florian Weigend3, Jose M Goicoechea2, Frank Tambornino3, Stephan Hohloch4. 1. Department of Chemistry and Center for Sustainable Systems Design (CSSD), Paderborn University, Warburger Strasse 100, 33098, Paderborn, Germany. 2. Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, UK. 3. Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35032, Marburg, Germany. 4. Institute for General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria.
Abstract
We present the η3 -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-N3 )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.
We present the η3 -coordination of the 2-phosphaethynthiolate anion in the complex (PN)2 La(pan class="Gene">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-N3 )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.
Authors: Grégoire Le Corre; Juan José Gamboa-Carballo; Zhongshu Li; Hansjörg Grützmacher Journal: Angew Chem Int Ed Engl Date: 2021-10-20 Impact factor: 16.823