Bis(chlorogermyliumylidene) and its significant role in elusive reductive cyclization

Abstract

Bis(chlorogermyliumylidene) 2 has been strategically obtained within redox-active bis(α-iminopyridine). Metal-free reduction of 2 followed by protonation led to elusive 2,3-di(pyridin-2-yl)piperazine with meso-stereoselectivity. Formation of persistent triplet diradicals upon reduction and isolation of piperazine stabilized Ge(ii) dication intermediates provide convincing evidence for the crucial role of [GeCl]+ units in reductive cyclization.

Coherent Solution‐phase Synthesis of a Germanium‐Graphitic Nanocomposite and Its Evaluation for Lithium‐Ion Battery Anodes: Non‐innocent Role of the Mashima Reagent

“…The reaction occurs in a single step and the volatile byproducts trimethylsilylchloride and pyrazine could be easily removed under vacuum yielding the heavier carbenes . This organosilicon reagent proved to be crucial for an elusive reductive cyclization step from bis(α‐iminopyridine) stabilized bis(chlorogermyliumylidene) …”

“…[6] This organosilicon reagent proved to be crucial for an elusive reductive cyclization step from bis(α-iminopyridine) stabilized bis(chlorogermyliumylidene). [7] In the nano regime, metal (0) particles have been achieved using this salt-free reduction method for both transition metal chlorides and also main-group chlorides (Ga, In, Sb and Bi). [8] Among the Group 14 elements, the nanoparticles of Ge are well-reputed to show a wide range of applications in the fields of optoelectronics, bio-imaging and energy conversion and storage.…”

Status of Inorganic Chemistry Research in India

“…6) (Bandyopadhyay et al, 1983). His research group also contributed significantly to the (Pal et al, 2016), (Sinhababu et al, 2016), (Majumdar et al, 2018) (Dhara et al, 2018) (Pahar et al, 2018).…”

Main‐Group Metal Complexes in Selective Bond Formations Through Radical Pathways

“…Salt‐free reduction of the dinuclear, dicationic germanium(II) compound 23 results in highly selective C−C bond formation through a (di‐)radical pathway and gives 24 after aqueous work‐up (Scheme ) . The dicationic diradical intermediate 23‐int‐1 was suggested based on EPR spectroscopic results.…”

“…Chelation control has been exploited in C−C bond formations in the coordination sphere of germanium for the synthesis of piperazine derivatives, as detailed in section 2.6 (Scheme ) . In addition, pinacol coupling has also been reported, starting from a redox‐active MIAN ligand ( 44 ) and Sn 0 to give Sn IV compound 45 (Scheme ) .…”