2019
DOI: 10.1002/anie.201908397
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Ring Contraction by NHC‐Induced Pnictogen Abstraction

Abstract: The reaction of [Cp'''Co(h 4 -P 4 )] (1)( Cp''' = 1,2,4-tBu 3 C 5 H 2 )w ith Me NHC ( Me NHC = 1,3,4,5-tetramethylimidazol-2-ylidene) leads through NHC-induced phosphorus cation abstraction to the ring contraction product [( Me NHC) 2 P]-[Cp'''Co(h 3 -P 3 )] (2), whichr epresents the first example of an anionic CoP 3 complex. Such NHC-induced ring contraction reactions are also applicable for triple-decker sandwichc omplexes.The complexes [(Cp*Mo) 2 (m,h 6:6 -E 6 )] (3a, 3b)(Cp* = C 5 Me 5 ;E = P, As) can be t… Show more

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Cited by 37 publications
(57 citation statements)
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“…The “functionalization by complexation” approach thus potentially enables the preparation of hitherto inaccessible and multiply substituted polyphosphorus scaffolds in the coordination sphere of transition‐metal cations. This strategy is complementary to previously reported methods for the synthesis of functionalized polyphosphorus complexes, and further extensions should give access to a broad range of novel P n frameworks.…”
Section: Figurementioning
confidence: 77%
“…The “functionalization by complexation” approach thus potentially enables the preparation of hitherto inaccessible and multiply substituted polyphosphorus scaffolds in the coordination sphere of transition‐metal cations. This strategy is complementary to previously reported methods for the synthesis of functionalized polyphosphorus complexes, and further extensions should give access to a broad range of novel P n frameworks.…”
Section: Figurementioning
confidence: 77%
“…[14] Ourf irst use of NHCs in their reactionst owards polyphosphorus complexesc ontaining cyclo-P 4 and cyclo-P 6 ligands as end-and as middle deck, respectively,s howedt hat Pa tom elimination reactions occur leadingt or ing contractionsi nw hich the NHCs act as strong nucleophilesa nd not as simple donor molecules. [15] Therefore, the question arises whether ar ing contraction would occur also towards the cyclo-P 5 ring in 1 resulting in an anionic cyclo-P 4 ligand complex of Fe for which ap recedent was recently reported ([Cp Ar Fe(h 4 -P 4 )] À ), [16] or whether unprecedented metastablen eutral adducts would result,r epresenting an ovel class of compounds, which, for the first time, might reveal no static structures in solution. This question is of general interest, sinceN HCs are known to react in deprotonation and dehydrocoupling reactions, respectively,E ÀHbond activationo rr ing opening towards main-group element compounds, depending on both the nature of the NHCa nd the feature (as for instance acidity) of the correspondingc ompound.…”
mentioning
confidence: 99%
“…H-Atome und Lçsungsmittelmoleküle wurden aus Gründen der Übersichtlichkeit weggelassen. [22] Abbildung 5. Resonanzstrukturen (I, II)d es NHC-Phosphiniden-Liganden.…”
Section: Interessenkonfliktunclassified
“…Die H-Atome und Lçsungsmittelmoleküle wurden aus Gründen der Übersichtlichkeit weggelassen. [22] Schema 3. Reaktion von [{Cp*Mo} 2 (m,h 6:6 -E 6 )] (E = P( 3a), As (3b)) mit Me NHC.…”
Section: Ringkontraktionsreaktionen Stellen In Der Organischenunclassified
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