Synthesis and reactivity of a six-membered heterocyclic 1,3-diphosphaallene.

Autor:	Sharma MK; Institute of Inorganic Chemistry, University of Duisburg-Essen Universitätsstraße 5-7 D-45141 Essen Germany stephan.schulz@uni-due.de https://www.uni-due.de/ak_schulz/index_en.php., Wölper C; Institute of Inorganic Chemistry, University of Duisburg-Essen Universitätsstraße 5-7 D-45141 Essen Germany stephan.schulz@uni-due.de https://www.uni-due.de/ak_schulz/index_en.php., Siera H; Institute of Organic Chemistry, University of Duisburg-Essen Universitätsstraße 5-7 D-45141 Essen Germany., Haberhauer G; Institute of Organic Chemistry, University of Duisburg-Essen Universitätsstraße 5-7 D-45141 Essen Germany., Schulz S; Institute of Inorganic Chemistry, University of Duisburg-Essen Universitätsstraße 5-7 D-45141 Essen Germany stephan.schulz@uni-due.de https://www.uni-due.de/ak_schulz/index_en.php.; Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen Carl-Benz-Straße 199 47057 Duisburg Germany.
Jazyk:	angličtina
Zdroj:	Chemical science [Chem Sci] 2024 Nov 29; Vol. 16 (3), pp. 1189-1196. Date of Electronic Publication: 2024 Nov 29 (Print Publication: 2025).
DOI:	10.1039/d4sc06371f
Abstrakt:	1,3-Diphosphaallenes are a new class of heavier heteroallenes and show a fascinating chemical behavior and reactivity. Herein we report on the room temperature transformation of gallaphosphene LGa(OCP)PGaL 1 (L = HC[C(Me)N(Ar)] 2 , Ar = 2,6-i-Pr 2 C 6 H 3 ) to the six-membered metallaheterocycle LGa(PCP)OGaL 2 featuring a LGa-substituted 1,3-diphosphaallene unit. The possible mechanism of formation of 2 is supported by quantum chemical calculations, which revealed that the formation of 2 is energetically more favorable ( ca. 2 kcal mol -1 ) than the formation of 1 at ambient temperature. Remarkably, 2 reacts with singlet carbenes selectively to new five-membered metallaheterocycles LGa(PC)OGaL(P)NHC (NHC = [CMeN(R)] 2 C; R = Me 3, i Pr 4; C{(NAr)CMe 2 CH 2 CMe 2 = cAAC (5) featuring a 1,3-diphospha-1,3-butadiene unit. In stark contrast, its reaction with trimethylsilyldiazomethane yields (LGa) 2 O(P 2 C 2 H)SiMe 3 6 featuring a 1,3-diphosphacyclobutene unit. Compounds 2-6 were characterized by heteronuclear NMR ( 1 H, 13 C, 31 P), UV-vis, and IR spectroscopy. Compounds 2-4 and 6 were also characterized by single crystal X-ray diffraction (sc-XRD) and their bonding nature was investigated by quantum chemical calculations. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
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