The capture,storage,and release of CO_(2)is one of the most pressing issues in chemistry.Herein,we designed bis(formazanate)magnesium complexes as precursors,which were synthesized by straightforward transamination be...The capture,storage,and release of CO_(2)is one of the most pressing issues in chemistry.Herein,we designed bis(formazanate)magnesium complexes as precursors,which were synthesized by straightforward transamination between the neutral formazan[PhNNC(4-tBuPh)NNHPh](LH)and[Mg{N(SiMe_(3))_(2)}_(2)].Depending on the solvent,either the homoleptic complex[L_(2)Mg]or the thf-coordinated complex[L_(2)Mg(thf)]was isolated.Reaction of the solvent-free complex[L_(2)Mg]with CO_(2)led to stoichiometric insertion into one of the four Mg–Nbonds with concomitant rearrangement of the ligand scaffold which adopts a trinuclear cagelike structure.The insertion reaction is reversible depending on thermolysis or treatment with tetrahydrofuran,which is corroborated by density functional theory calculations.This showcases the first example of reversible uptake of CO_(2)by an s-block coordination compound.展开更多
We have discovered a route to access the longest low-valent molecular silaphospha-chain,a sevenmembered chain structure that incorporates three silicon and four phosphorus atoms by stepwise activation of white phospho...We have discovered a route to access the longest low-valent molecular silaphospha-chain,a sevenmembered chain structure that incorporates three silicon and four phosphorus atoms by stepwise activation of white phosphorus(P_(4))using two different silylene precursors.The chain species was formed via a highly reactive polyphosphide intermediate.The isolation of a stable analogue of this reaction intermediate was achieved by stepwise reaction with mono and bis(silylenes).Due to the rigidity of the ferrocenediyl framework of the bis(silylene),the isomerization process of the chain structure was hampered.Theoretical studies such as natural bond orbital and atoms in molecules analyses of the seven-membered chain species indicated some degree of delocalization of the double bond system.展开更多
基金D.J.thanks the China Scholarship Council(grant no.201906030178)for generous supportWe also acknowledge support by the state of Baden-Württemberg through bwHPC and DFG through grant no.INST 40/467-1 FUGG(JUSTUS cluster).
文摘The capture,storage,and release of CO_(2)is one of the most pressing issues in chemistry.Herein,we designed bis(formazanate)magnesium complexes as precursors,which were synthesized by straightforward transamination between the neutral formazan[PhNNC(4-tBuPh)NNHPh](LH)and[Mg{N(SiMe_(3))_(2)}_(2)].Depending on the solvent,either the homoleptic complex[L_(2)Mg]or the thf-coordinated complex[L_(2)Mg(thf)]was isolated.Reaction of the solvent-free complex[L_(2)Mg]with CO_(2)led to stoichiometric insertion into one of the four Mg–Nbonds with concomitant rearrangement of the ligand scaffold which adopts a trinuclear cagelike structure.The insertion reaction is reversible depending on thermolysis or treatment with tetrahydrofuran,which is corroborated by density functional theory calculations.This showcases the first example of reversible uptake of CO_(2)by an s-block coordination compound.
基金supported by the Deutsche Forschungsgemeinschaft(DFG)[project no.470309834(Ro2008/21-1 and HI 2063/1-1)]the support by the state of Baden-Württemberg through bwHPC and DFG[grant no.INST 40/467-1 FUGG(JUSTUS cluster)].
文摘We have discovered a route to access the longest low-valent molecular silaphospha-chain,a sevenmembered chain structure that incorporates three silicon and four phosphorus atoms by stepwise activation of white phosphorus(P_(4))using two different silylene precursors.The chain species was formed via a highly reactive polyphosphide intermediate.The isolation of a stable analogue of this reaction intermediate was achieved by stepwise reaction with mono and bis(silylenes).Due to the rigidity of the ferrocenediyl framework of the bis(silylene),the isomerization process of the chain structure was hampered.Theoretical studies such as natural bond orbital and atoms in molecules analyses of the seven-membered chain species indicated some degree of delocalization of the double bond system.
