An Isolable Bis(Germylene)‐Stabilized Plumbylone

Abstract

We report herein the synthesis of a stable plumbylone (3) by reduction of a bromodigermylplumbylene (2) with 2.2 equiv of potassium graphite (KC 8 ). The molecular structure of 3 was established by a singlecrystal X-ray diffraction study and features a twocoordinated Pb center with an acute GeÀ PbÀ Ge bond angle. Computational studies showed that this complex (3) possesses a singlet electronic ground state with a Pb 0 center. Its high thermal stability can be most likely ascribed to the delocalization of π electrons over the GeÀ PbÀ Ge moiety. A preliminary reactivity study demonstrates that complex 3 can deliver Pb 0 atoms to an organic azide producing a tetrameric imido complex [(PbNDipp) 4 ] (Dipp = 2,6-i Pr-C 6 H 3 , 4) and perform a metathesis reaction with GeCl 2 •dioxane to produce a bis(germylene)-stabilized germylone (5), highlighting the synthetic utility of 3.

Counterintuitive Chemistry: Carbene Stabilization of Zero-Oxidation State Main Group Species

“…Despite encouraging computational efforts, , carbene-stabilized stannylones and plumbylones have not been experimentally realized. The recent synthesis of bis­(silylene)- or bis­(germylene)-stabilized plumbylones may inspire synthetic chemists to finally prepare the corresponding carbene analogs. , …”

“… Due to the redox-active character of the dithiolene ligand, the silicon atom is oxidized from the oxidation state of zero (in 28 ) to +4 (in 31 ). 28 acts as a silicon-transfer agent in this transformation, which joins a group of single-E-species-transfer reactions (such as E = N, P, , Si, Al, and Pb).…”

“…•+ radical cation (65), ferrocenium triflate mediated two-electron oxidation of 59 gave the NHCstabilized P 2 2+ dication (66) (Scheme 18). 123 This laboratory subsequently discovered that the Lewis acid GaCl 3 may be employed as an oxidant to convert NHCstabilized As 2 (0) (61) into either the corresponding monocationic diarsenic radical (67) or the dicationic diarsene (68) (Scheme 19).…”

“…The recent synthesis of bis(silylene)or bis(germylene)-stabilized plumbylones may inspire synthetic chemists to finally prepare the corresponding carbene analogs. 64,65 Dutton's computations concerning carbene-stabilization of monatomic Be(0) and diatomic Be 2 (0) species 66 suggested that carbene-complexed beryllium(0) complexes are considerably more stable than the corresponding magnesium(0) analogues. Braunschweig reported the first carbene-stabilized beryllium(0) complexes, (CAAC) 2 Be(0) (26 and 27) in 2016, via the potassium graphite reduction of CAAC-BeCl 2 complexes (24 and 25), respectively (Scheme 8).…”

Reactions of main group compounds with azides forming organic nitrogen-containing species

“…In 2022, Zhao, Mo and co-workers synthesized the first stable plumbylone and explored its reaction with azides (Scheme 111). 177 Pb5 reacts with DipN 3 in benzene at room temperature to afford the tetrameric imido complex Pb5-P in high yield with the release of N 2 . The authors propose the mechanism involving the initial formation of lead imide intermediate, followed by the ligand dissociation and subsequent tetramerization to yield the final product Pb5-P .…”