The first zwitterionic borata-bis(NHC)-stabilized phosphaketenyl germyliumylidene [(L (O=C=P)Ge:] 2 (L =(p-tolyl) B[1-(1-adamantyl)-3-yl-2-ylidene] ) has been synthesized by salt-metathesis reaction of [L (Cl)Ge:] 1 with sodium phosphaethynolate [(dioxane) NaOCP]. Unexpectedly, its exposure to UV light affords, after reductive elimination of the entire PCO group, the unprecedented [L Ge-GeL ] complex 3 in 54 % yields bearing the Ge ion with Ge in the oxidation state +1. In addition, the 1,3-digermylium-2,4-diphosphacyclobutadiene [L Ge(μ-P) GeL ] 4 and bis(germyliumylidenyl)-substituted diphosphene [(L Ge-P=P-GeL )] 5 could also be obtained in moderate yields. The formation of 3-5 and their electronic structures have been elucidated with DFT calculations.
A facile, one-pot synthesis of [Na(OC≡As)(dioxane) ] (x=2.3-3.3) in 78 % yield is reported through the reaction of arsine gas with dimethylcarbonate in the presence of NaO Bu and 1,4-dioxane. It has been employed for the synthesis of the first arsaketenyl-functionalized germylene [LGeAsCO] (2, L=CH[CMeN(Dipp)] ; Dipp=2,6- Pr C H ) from the reaction with LGeCl (1). Upon exposure to ambient light, 2 undergoes CO elimination to form the 1,3-digerma-2,4-diarsacyclobutadiene [L Ge As ] (3), which contains a symmetric Ge As ring with ylide-like Ge=As bonds. Remarkably, the CO ligand located at the arsenic center of 2 can be exchanged with PPh or an N-heterocyclic carbene NHC donor ( NHC=1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) to afford the novel germylidenylarsinidene complexes [LGe-AsPPh ] (4) and [LGe-As( NHC)] (5), respectively, demonstrating transition-metal-like ligand substitution at the arsinidene-like As atom. The formation of 2-5 and their electronic structures have been studied by DFT calculations.
A facile, one‐pot synthesis of [Na(OC≡As)(dioxane)x] (x=2.3–3.3) in 78 % yield is reported through the reaction of arsine gas with dimethylcarbonate in the presence of NaOtBu and 1,4‐dioxane. It has been employed for the synthesis of the first arsaketenyl‐functionalized germylene [LGeAsCO] (2, L=CH[CMeN(Dipp)]2; Dipp=2,6‐iPr2C6H3) from the reaction with LGeCl (1). Upon exposure to ambient light, 2 undergoes CO elimination to form the 1,3‐digerma‐2,4‐diarsacyclobutadiene [L2Ge2As2] (3), which contains a symmetric Ge2As2 ring with ylide‐like Ge=As bonds. Remarkably, the CO ligand located at the arsenic center of 2 can be exchanged with PPh3 or an N‐heterocyclic carbene iPrNHC donor (iPrNHC=1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) to afford the novel germylidenylarsinidene complexes [LGe‐AsPPh3] (4) and [LGe‐As(iPrNHC)] (5), respectively, demonstrating transition‐metal‐like ligand substitution at the arsinidene‐like As atom. The formation of 2–5 and their electronic structures have been studied by DFT calculations.
The decarbonylation of the first zinco(ii) arsaketene complexes LZnAsCO (2) and LZn(AsCO)(NHC) (4) (L = {CH(CMeNDipp)2}-, Dipp = 2,6-iPr2C6H3; NHC = [C(Me)N(iPr)]2C:) has been investigated in the presence of the N-heterocyclic silylenes, tBuNHSi (tBuNHSi = [C(H)N(tBu)]2Si:) and DippNHSi (DippNHSi = [C(H)N(2,6-iPr2-C6H3)]2Si:). Depending on the steric demand of the NHSi donor, dimers or monomers of silylene-stabilised arsinidenes are isolated. The bonding situations in all of the novel arsinidene complexes have been elucidated through X-ray diffraction analyses and theoretical calculations.
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