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η3 -Coordination and Functionalization of the 2-Phosphaethynthiolate Anion at Lanthanum(III)*.

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.

SUBMITTER: Watt FA 

PROVIDER: S-EPMC8252525 | biostudies-literature | 2021 Apr

REPOSITORIES: biostudies-literature

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η<sup>3</sup> -Coordination and Functionalization of the 2-Phosphaethynthiolate Anion at Lanthanum(III)*.

Watt Fabian A FA   Burkhardt Lukas L   Schoch Roland R   Mitzinger Stefan S   Bauer Matthias M   Weigend Florian F   Goicoechea Jose M JM   Tambornino Frank F   Hohloch Stephan S  

Angewandte Chemie (International ed. in English) 20210311 17

We present the η<sup>3</sup> -coordination of the 2-phosphaethynthiolate anion in the complex (PN)<sub>2</sub> La(SCP) (2) [PN=N-(2-(diisopropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide)]. Structural comparison with dinuclear thiocyanate-bridged (PN)<sub>2</sub> La(μ-1,3-SCN)<sub>2</sub> La(PN)<sub>2</sub> (3) and azide-bridged (PN)<sub>2</sub> La(μ-1,3-N<sub>3</sub> )<sub>2</sub> La(PN)<sub>2</sub> (4) complexes indicates that the [SCP]<sup>-</sup> coordination mode is mainly governed  ...[more]

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