The bis(phosphine)-functionalizedβ-diketiminate ligand[HC{(CH_(3))C}_(2){(o-[P(C_(6)H_(5))_(2)]_(2)C_(6)H_(4))N}_(2)]^(−)(PNac)was used for the synthesis of luminescent closed-shell bimetallic complexes.The PNNP pock...The bis(phosphine)-functionalizedβ-diketiminate ligand[HC{(CH_(3))C}_(2){(o-[P(C_(6)H_(5))_(2)]_(2)C_(6)H_(4))N}_(2)]^(−)(PNac)was used for the synthesis of luminescent closed-shell bimetallic complexes.The PNNP pocket combin ing both soft and hard donor sites can act as an orthogonal ligand scaffold to selectively coordinate two different metal ions.Deprotonation and subsequent salt elimination with[AuCl(tht)](tht=tetrahydrothio phene)or AgI yielded the mononuclear complexes[PNacAu](1)or[PNacAg](2),respectively.The Au^(Ⅰ)ion is linearly coordinated by the two phosphines,forming a 12-membered metalla-macrocycle with an emptyß-diketiminate pocket available for complexation of hard d10 metal ions(Zn^(Ⅱ),Cd^(Ⅱ),and Hg^(Ⅱ)).According to this synthetic protocol,a series of heterobimetallic complexes were isolated.The complexa tion of the second metal ion in close spatial proximity has led to drastic changes in the photophysical pro perties.For further studies and understanding,quantum chemical calculations were performed.展开更多
Herein,we present the first report of coumarin-based phosphinoamine ligands[CoumPNH]and their gold(Ⅰ)complexes.The deprotonation and chloride abstraction from phosphinoamine gold(Ⅰ)complexes[(CoumPNH)Au^(Ⅰ)Cl]led t...Herein,we present the first report of coumarin-based phosphinoamine ligands[CoumPNH]and their gold(Ⅰ)complexes.The deprotonation and chloride abstraction from phosphinoamine gold(Ⅰ)complexes[(CoumPNH)Au^(Ⅰ)Cl]led to the unexpected formation of polynuclear gold(Ⅰ)metallacycles.The size of the cycles depends on the steric bulk of the phosphine groups.The gold(Ⅰ)metallacycles feature only weak intramolecular aurophilic interactions and do not exhibit intermolecular interactions.Additionally,these metallacycles show significant luminescent properties.Quantum chemical calculations support the photophysical properties of the complexes.Notably,these compounds are the first polynuclear cyclic rings bridged by phosphinoamide ligands.Moreover,the reactivity of the cyclic compounds was explored in this study.展开更多
As heavier aromatic analogs of the cyclopentadienides,group 14 dianionic metalloles exhibit more versatile reactivity and coordination modes due to the additional lone pair at the heteroatom.Compared to the well-estab...As heavier aromatic analogs of the cyclopentadienides,group 14 dianionic metalloles exhibit more versatile reactivity and coordination modes due to the additional lone pair at the heteroatom.Compared to the well-established chemistry of monoanionic cyclopentadienide ligands,the coordination chemistry with those dianionic ligands remains underexplored.This perspective provides an overview of literature-known examples of group 14 metallole dianions(silole,germole,stannole and plumbole)adoptingη^(5)-coordinating modes.展开更多
The iminophosphonamide[R2P(NR’)2]−ligand is an analog of phosphate(R2PO2−),replacing its oxygen atoms with two amide groups.This review aims to provide the first comprehensive report on coordination chemistry dealing...The iminophosphonamide[R2P(NR’)2]−ligand is an analog of phosphate(R2PO2−),replacing its oxygen atoms with two amide groups.This review aims to provide the first comprehensive report on coordination chemistry dealing with iminophosphonamide ligands,focusing on the s-block,p-block,transition,and f-block metals.In particular,this monoanionic ligand’s coordination mode and reactivity with the metal centers are discussed.The last section of the review is dedicated to the reported chiral iminophosphonamine ligands and corresponding metal complexes.展开更多
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Deutsche Forschungsgemeinschaft(DFG)for financial support through the Transregional Collaborative Research Centre CRC/TRR 88“Cooperative Effects in Homo-and Heterometallic Complexes(3MET)”(Projects C1 and C3).
文摘The bis(phosphine)-functionalizedβ-diketiminate ligand[HC{(CH_(3))C}_(2){(o-[P(C_(6)H_(5))_(2)]_(2)C_(6)H_(4))N}_(2)]^(−)(PNac)was used for the synthesis of luminescent closed-shell bimetallic complexes.The PNNP pocket combin ing both soft and hard donor sites can act as an orthogonal ligand scaffold to selectively coordinate two different metal ions.Deprotonation and subsequent salt elimination with[AuCl(tht)](tht=tetrahydrothio phene)or AgI yielded the mononuclear complexes[PNacAu](1)or[PNacAg](2),respectively.The Au^(Ⅰ)ion is linearly coordinated by the two phosphines,forming a 12-membered metalla-macrocycle with an emptyß-diketiminate pocket available for complexation of hard d10 metal ions(Zn^(Ⅱ),Cd^(Ⅱ),and Hg^(Ⅱ)).According to this synthetic protocol,a series of heterobimetallic complexes were isolated.The complexa tion of the second metal ion in close spatial proximity has led to drastic changes in the photophysical pro perties.For further studies and understanding,quantum chemical calculations were performed.
基金support within the project 540378534,RO 2008/22-1.
文摘Herein,we present the first report of coumarin-based phosphinoamine ligands[CoumPNH]and their gold(Ⅰ)complexes.The deprotonation and chloride abstraction from phosphinoamine gold(Ⅰ)complexes[(CoumPNH)Au^(Ⅰ)Cl]led to the unexpected formation of polynuclear gold(Ⅰ)metallacycles.The size of the cycles depends on the steric bulk of the phosphine groups.The gold(Ⅰ)metallacycles feature only weak intramolecular aurophilic interactions and do not exhibit intermolecular interactions.Additionally,these metallacycles show significant luminescent properties.Quantum chemical calculations support the photophysical properties of the complexes.Notably,these compounds are the first polynuclear cyclic rings bridged by phosphinoamide ligands.Moreover,the reactivity of the cyclic compounds was explored in this study.
基金Deutsche Forschungsgemeinschaft(DFG)is acknowledged for financial support within the Reinhart Koselleck-Projekt 440644676,RO 2008/19-1.
文摘As heavier aromatic analogs of the cyclopentadienides,group 14 dianionic metalloles exhibit more versatile reactivity and coordination modes due to the additional lone pair at the heteroatom.Compared to the well-established chemistry of monoanionic cyclopentadienide ligands,the coordination chemistry with those dianionic ligands remains underexplored.This perspective provides an overview of literature-known examples of group 14 metallole dianions(silole,germole,stannole and plumbole)adoptingη^(5)-coordinating modes.
基金supported by the German Research Foundation(DFG)through grant no.546228048(RO 2008/25-1).
文摘The iminophosphonamide[R2P(NR’)2]−ligand is an analog of phosphate(R2PO2−),replacing its oxygen atoms with two amide groups.This review aims to provide the first comprehensive report on coordination chemistry dealing with iminophosphonamide ligands,focusing on the s-block,p-block,transition,and f-block metals.In particular,this monoanionic ligand’s coordination mode and reactivity with the metal centers are discussed.The last section of the review is dedicated to the reported chiral iminophosphonamine ligands and corresponding metal complexes.
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.
