The Reactivity of Germanium Phosphanides with Chalcogens

Abstract

The reactivity of germanium phosphanido complexes with elemental chalcogens is reported. Addition of sulfur to [(BDI)GePCy] (BDI = CH{(CH)CN-2,6-iPrCH}) results in oxidation at germanium to form germanium(IV) sulfide [(BDI)Ge(S)PCy] and oxidation at both germanium and phosphorus to form germanium(IV) sulfide dicylohexylphosphinodithioate complex [(BDI)Ge(S)SP(S)Cy], whereas addition of tellurium to [(BDI)GePCy] only gives the chalcogen inserted product, [(BDI)GeTePCy]. This reactivity is different from that observed between [(BDI)GePCy] and selenium. Addition of selenium to the diphenylphosphanido germanium complex, [(BDI)GePPh], results in insertion of selenium into the Ge-P bond to form [(BDI)GeSePCy] as well as the oxidation at phosphorus to give [(BDI)GeSeP(Se)Ph]. In contrast, addition of selenium to the bis(trimethylsilyl)phosphanido germanium complex, [(BDI)GeP(SiMe)], yields the germanium(IV) selenide [(BDI)Ge(Se)P(SiMe)].

N-Heterocyclic Carbene-Stabilized Germa-acylium Ion: Reactivity and Utility in Catalytic CO2 Functionalizations

“…The Ge–S bond length in 5­[BArF] (2.104(7) Å) is close to those of donor-stabilized GeS bonds (ranging from 2.053 to 2.095 Å) and shorter than the typical Ge–S single bond length (2.239 Å) (Figure ). ,− Similarly, the Ge–Se bond length in 6­[BArF] (2.2372(5) Å) is sufficiently shorter than a Ge–Se single bond (2.461 Å) and falls within the range of tetracoordinated donor-stabilized GeSe bonds (Figure ). , The Ge–S and Ge–Se bonds in compounds 5 and 6 are longer than the kinetically stabilized tricoordinate GeS and GeSe bonds, respectively .…”

“…46,[59][60][61][62][63][64] Similarly, the Ge-Se bond length in 6[BArF] (2.237 (5) Å) is sufficiently shorter than a Ge-Se single bond (2.461 Å) and falls within the range of tetracoordinated donor stabilized Ge=Se bonds (Figure 5). [60][61] The Ge-S and Ge-Se bond in compound 5 and 6, are longer than the kinetically stabilized tricoordinate Ge=S and Ge=Se bonds, respectively. 65 Notably, compound 6[BArF] represents the first example of cationic germaselenium complex.…”

Modern Techniques in Synthesis of Organometallic Compounds of Germanium

“…After filtration, the reaction mixture was concentrated under vacuum. Mixture was stored for 24 h at −27°C to obtain red crystals of the product [4]. After reaction mixture was placed overnight at room temperature, volatiles were removed in vacuum and crude product was distilled at 10 −1 torr to afford pure complex.…”

“…GST (Ge 2 Sb 2 Te 5 ) mainly is a well-liked phase-change substance for phase-change random access memory devices [3]. Group 14 elements have extensive variety of application from photovoltaic devices to PRAM material [4].…”

Bonding and Reactivity of Gallium and Aluminium Coordination Complexes

“…Following heating to 40 °C for 2 hours, the 1 H NMR spectrum showed a new γ-proton resonance at δ 4.90 ppm in a 3:7 ratio to the starting material (Figure 120), heating to 60 °C for 2 hours increased the amount of this product formed, however continued heating at 60 °C for 16 hours lead to the formation of a second γ-proton resonance at δ 4.81 ppm, in addition to the first product observed, in a 65:35 ratio and complete consumption of the starting material. Chalcogens are known to insert into metal-phosphorus bonds, 281 can oxidise P(III) complexes to P(V), [281][282] and can also insert into phosphorus-hydrogen bonds, 282 and any combination of these three reactions could account for the two products 81a-g (Scheme 67).…”