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

IF 7.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Chemical Science Pub Date : 2024-11-29 DOI:10.1039/d4sc06371f

Mahendra K. Sharma, Christoph Wölper, Hannah Siera, Gebhard Haberhauer, Stephan Schulz

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Abstract

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-Pr2C6H3) 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) than 1 at ambient temperature. Remarkably, 2 reacts with singlet carbenes selectively to new five-membered metallaheterocycles LGa(PC)OGaL(P)NHC (NHC = [CMeN(R)]2C; R = Me 3, iPr 4; C{(NAr)CMe2CH2CMe2 = cAAC 5) featuring a 1,3-diphospha-1,3-butadiene unit. In stark contrast, its reaction with trimethylsilyldiazomethane yields (LGa)2O(P2C2H)SiMe3 6 featuring a 1,3-diphosphacyclobutene unit. Compounds 2‒6 were characterized by heteronuclear NMR (1H, 13C, 31P), 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.

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来源期刊

Chemical Science CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

4.80%

发文量

1352

审稿时长

2.1 months

期刊介绍： Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.