A novel indolyl-based NCN pincer ligand precursor HL(HL=(1-(2-(CH_(2))_(4)NCH_(2)CH_(2))-3-(2,6-ipr_(2)C_(6)H_(3)N=CH)C_(8)H_(5)N))was rationally and precisely designed,and successfully prepared in a high yield.Lithia...A novel indolyl-based NCN pincer ligand precursor HL(HL=(1-(2-(CH_(2))_(4)NCH_(2)CH_(2))-3-(2,6-ipr_(2)C_(6)H_(3)N=CH)C_(8)H_(5)N))was rationally and precisely designed,and successfully prepared in a high yield.Lithiation of HL with^(n)BuLi in n-hexane,followed by treatment with RECl_(3)in THF led to the isolation of rare-earth metal chlorides in monomeric form(κ^(3)-L)RECI_(2)(THF)(RE=Sc(2),Yb(3)),and dimeric form[(κ^(3)-L)RECI(THF)(μ-Cl)]_(2)(RE=Er(4),Y(5))bearing the novel indolyl-based NCN pincer ligand in designed pincer ligation depending on different metal ionic radii;and the chloride bridged rare-earth metal and lithium mixed complexes in form(κ^(2)-L)_(2)RE(μ-Cl)_(2)Li(THF)_(2)(RE=Y(6),Dy(7)).All complexes were fully characterized and their structures were determined.The diamagnetic complexes 2,5 and 6 were furtherly characterized by the NMR spectroscopic method.The catalytic activity studies revealed that the central metal ions,borates,aluminum alkyls,and ligation of the central metal ions have influences on catalytic activity,and regio-and stereoselectivity for the polymerization of isoprene.With cooperation of the cocatalysts,the pincer-type yttrium chloride 5 initiated the isoprene polymerization with a high activity producing polymers with high regio-and stereoselectivity(1,4-cis polymers up to 99.6%),and the Mn as high as 8.76×10^(5).展开更多
A series of dinuclear rare-earth metal alkyl complexes{[μ-η^2:η^1:η^1-3-(LNCH)(CH2SiMe3)Ind]RE-(CH2SiMe3)(THF)}2(L^1=2-tBuC6H4,RE=Y,Gd,Dy,Er,Yb;L^2=2,4,6-Me3C6H2,RE=Dy,Er;Ind=indolyl)and{[μ-η^2:η^1:η^1-3-(LNCH...A series of dinuclear rare-earth metal alkyl complexes{[μ-η^2:η^1:η^1-3-(LNCH)(CH2SiMe3)Ind]RE-(CH2SiMe3)(THF)}2(L^1=2-tBuC6H4,RE=Y,Gd,Dy,Er,Yb;L^2=2,4,6-Me3C6H2,RE=Dy,Er;Ind=indolyl)and{[μ-η^2:η^1:η^1-3-(LNCH2)Ind]RE(CH2SiMe3)(THF)}2(L^1,RE=Y,Dy,Er,Yb;L^2,RE=Er,Yb)bearing 3-arylamido functionalized indolyl ligands having diverse bonding modes with metal ions were synthesized either by the insertion reaction of the imino group to the RE-C bond or by the alkane elimination reaction.In the preparation of above complexes,rare-earth metal alkyl complexes{[μ-η^5:η^1:η^1-3-(L^2 NCH)(CH2SiMe3)Ind]Gd(CH2SiMe3)(THF)}2 with aμ-η^5:η^1:η^1 coordination mode to the gadolinium ion and{[μ-η^3:η^1:η^1-3-(L^2NCH2)Ind]Dy(CH2SiMe3)(THF)}2 with aμ-η^3:η^1:η^1 coordination mode to the dysprosium ion were unexpectedly isolated.The reactions of 3-(L^2N=CH)lnd with Er(CH2SiMe3)3(THF)2 at room temperature,generated a tetranuclear imino-indolyl erbium intermediate{[μ-η^1:η^1-3-(L^2N=CH)Ind]Er(CH2SiMe3)2(THF)}4,which can transform into the amido functionalized indolyl erbium complex in hot toluene.Moreover,the reactivities of the newly synthesized ytterbium complex with N-heterocyclic compounds were investigated,affording the corresponding products of the mixed pyridyl-indolyl,imidazolyl-indolyl,and ortho-metalated complexes.The yttrium complexes showed a high regioselectivity and steroselectivity for the isoprene polymerization with 1,4-trans selectivity up to 91.7%and 1,4-cis selectivity up to 96.1%in the presence of cocatalysts,respectively.展开更多
Ligands play a key role in controlling activity of organometallic complexes so that development of new ligands to overcome the challenge is the main topic of modern chemistry.The first example of 1,1-hydride migratory...Ligands play a key role in controlling activity of organometallic complexes so that development of new ligands to overcome the challenge is the main topic of modern chemistry.The first example of 1,1-hydride migratory insertion and intramolecular redox reaction has been realized in this work by applying a new ligand in rare-earth metal chemistry.The novel rare-earth metal complexes L^(Mes)RECH2TMS(THF)(RE=Y(1a),Dy(1b),Er(1c),Yb(1d),L^(Mes)=1-(3-(2,6-iPr_(2)C_(6)H_(3)N=CH)C8H4N)-CH_(2)CH_(2)-3-(2-CH2–4,6-Me_(2)C_(6)H_(2))-(N(CH)_(2)NC),THF=tetrahydrofuran)bearing a ligand with imino,indolyl,NHC(N-heterocyclic carbene)multiple functionalities were synthesized and characterized.Treatment of complexes 1 with silanes(PhSiH3or PhSiH2Me or PhSiD3)selectively produced the unprecedented 1,1-hydride(or deuterated H)migratory insertion of the indolyl moiety of the novel unsymmetrical dinuclear rare-earth metal complexes 2.The complex 2a reacts with Ph_(2)C=O to give the selective C=O double bond insertion to the RE–Co-methylene-Mesbond product 3a which further reacts with another Ph_(2)C=O(or DMAP,4-N,N-dimethylaminopyridine)affording the novelμ-η^(2):η^(3)-dianionic 3-iminoindolyl dinuclear rare-earth metal complex 4a.The latter is formed through an unusual intramolecular redox reaction(through electron migration from the 2-carbanion of the indolyl ring to the imino motif)resulting in the re-aromatization of the indolyl ring.展开更多
The resource trade-off between growth and immunity is common in plants,but the underlying molecular mechanisms remain unclear.In this study,we demonstrate that the posttranslational regulation of the Target of Rapamyc...The resource trade-off between growth and immunity is common in plants,but the underlying molecular mechanisms remain unclear.In this study,we demonstrate that the posttranslational regulation of the Target of Rapamycin(TOR)kinase is a key determinant in maintaining this balance.Inhibiting TOR activity,either pharmacologically or genetically,enhanced root immunity and mitigated pathogen-induced root growth suppression.ToR inactivation preceded resource depletion during the early stage of infection,indicating an active resource reallocation mechanism that prioritizes defense activation over growth maintenance.Mechanistic studies uncovered a phosphorylation circuit where pathogen recognition activates the lectin receptor-like kinase LORE,which stimulates the phosphatase LOPP to directly dephosphorylate and inactivate TOR.Subsequently,LOPP is degraded via a proteasomal pathway,restoring TOR activity.This phosphorylation circuit enables plants to prioritize immune responses while maintaining growth flexibility.Our findings establish TOR as a key regulator of resource allocation during host-microbe interactions and offer a mechanistic framework for understanding growth-immunity trade-offs in plants.展开更多
基金Financial support for this work was provided by the National Natural Science Foundation of China(Nos.21432001,21871004,21861162009)the grants from Anhui Province(2017D107).
文摘A novel indolyl-based NCN pincer ligand precursor HL(HL=(1-(2-(CH_(2))_(4)NCH_(2)CH_(2))-3-(2,6-ipr_(2)C_(6)H_(3)N=CH)C_(8)H_(5)N))was rationally and precisely designed,and successfully prepared in a high yield.Lithiation of HL with^(n)BuLi in n-hexane,followed by treatment with RECl_(3)in THF led to the isolation of rare-earth metal chlorides in monomeric form(κ^(3)-L)RECI_(2)(THF)(RE=Sc(2),Yb(3)),and dimeric form[(κ^(3)-L)RECI(THF)(μ-Cl)]_(2)(RE=Er(4),Y(5))bearing the novel indolyl-based NCN pincer ligand in designed pincer ligation depending on different metal ionic radii;and the chloride bridged rare-earth metal and lithium mixed complexes in form(κ^(2)-L)_(2)RE(μ-Cl)_(2)Li(THF)_(2)(RE=Y(6),Dy(7)).All complexes were fully characterized and their structures were determined.The diamagnetic complexes 2,5 and 6 were furtherly characterized by the NMR spectroscopic method.The catalytic activity studies revealed that the central metal ions,borates,aluminum alkyls,and ligation of the central metal ions have influences on catalytic activity,and regio-and stereoselectivity for the polymerization of isoprene.With cooperation of the cocatalysts,the pincer-type yttrium chloride 5 initiated the isoprene polymerization with a high activity producing polymers with high regio-and stereoselectivity(1,4-cis polymers up to 99.6%),and the Mn as high as 8.76×10^(5).
基金The authors gratefully acknowledge the National Natural Science Foundation of China(Nos.21871004,21432001,21861162009 and 21672003).
文摘A series of dinuclear rare-earth metal alkyl complexes{[μ-η^2:η^1:η^1-3-(LNCH)(CH2SiMe3)Ind]RE-(CH2SiMe3)(THF)}2(L^1=2-tBuC6H4,RE=Y,Gd,Dy,Er,Yb;L^2=2,4,6-Me3C6H2,RE=Dy,Er;Ind=indolyl)and{[μ-η^2:η^1:η^1-3-(LNCH2)Ind]RE(CH2SiMe3)(THF)}2(L^1,RE=Y,Dy,Er,Yb;L^2,RE=Er,Yb)bearing 3-arylamido functionalized indolyl ligands having diverse bonding modes with metal ions were synthesized either by the insertion reaction of the imino group to the RE-C bond or by the alkane elimination reaction.In the preparation of above complexes,rare-earth metal alkyl complexes{[μ-η^5:η^1:η^1-3-(L^2 NCH)(CH2SiMe3)Ind]Gd(CH2SiMe3)(THF)}2 with aμ-η^5:η^1:η^1 coordination mode to the gadolinium ion and{[μ-η^3:η^1:η^1-3-(L^2NCH2)Ind]Dy(CH2SiMe3)(THF)}2 with aμ-η^3:η^1:η^1 coordination mode to the dysprosium ion were unexpectedly isolated.The reactions of 3-(L^2N=CH)lnd with Er(CH2SiMe3)3(THF)2 at room temperature,generated a tetranuclear imino-indolyl erbium intermediate{[μ-η^1:η^1-3-(L^2N=CH)Ind]Er(CH2SiMe3)2(THF)}4,which can transform into the amido functionalized indolyl erbium complex in hot toluene.Moreover,the reactivities of the newly synthesized ytterbium complex with N-heterocyclic compounds were investigated,affording the corresponding products of the mixed pyridyl-indolyl,imidazolyl-indolyl,and ortho-metalated complexes.The yttrium complexes showed a high regioselectivity and steroselectivity for the isoprene polymerization with 1,4-trans selectivity up to 91.7%and 1,4-cis selectivity up to 96.1%in the presence of cocatalysts,respectively.
基金supported by the National Natural Science Foundation of China(22031001,21871004,21861162009,22171004)the grants from the Education Department of Anhui Province(GXXT-2021-052)。
文摘Ligands play a key role in controlling activity of organometallic complexes so that development of new ligands to overcome the challenge is the main topic of modern chemistry.The first example of 1,1-hydride migratory insertion and intramolecular redox reaction has been realized in this work by applying a new ligand in rare-earth metal chemistry.The novel rare-earth metal complexes L^(Mes)RECH2TMS(THF)(RE=Y(1a),Dy(1b),Er(1c),Yb(1d),L^(Mes)=1-(3-(2,6-iPr_(2)C_(6)H_(3)N=CH)C8H4N)-CH_(2)CH_(2)-3-(2-CH2–4,6-Me_(2)C_(6)H_(2))-(N(CH)_(2)NC),THF=tetrahydrofuran)bearing a ligand with imino,indolyl,NHC(N-heterocyclic carbene)multiple functionalities were synthesized and characterized.Treatment of complexes 1 with silanes(PhSiH3or PhSiH2Me or PhSiD3)selectively produced the unprecedented 1,1-hydride(or deuterated H)migratory insertion of the indolyl moiety of the novel unsymmetrical dinuclear rare-earth metal complexes 2.The complex 2a reacts with Ph_(2)C=O to give the selective C=O double bond insertion to the RE–Co-methylene-Mesbond product 3a which further reacts with another Ph_(2)C=O(or DMAP,4-N,N-dimethylaminopyridine)affording the novelμ-η^(2):η^(3)-dianionic 3-iminoindolyl dinuclear rare-earth metal complex 4a.The latter is formed through an unusual intramolecular redox reaction(through electron migration from the 2-carbanion of the indolyl ring to the imino motif)resulting in the re-aromatization of the indolyl ring.
基金supported by the Key Research and Development Program of Zhejiang Province,China(2021C02064-7 and 2024SSYS0104)the National Natural Science Foundation of China(32470284 and 32270289)+4 种基金the Natural Science Foundation of Zhejiang Province,China(Z25C140005)the National Key Research and Development Program of China(2023YFD1902903)to Y.L.ANPCyT(PICT2021-0514)ANID-Programa Iniciativa Científica Milenio ICN17_022the Fondo Nacional de Desarrollo Científico y Tecnológico(1250304)to J.M.E.
文摘The resource trade-off between growth and immunity is common in plants,but the underlying molecular mechanisms remain unclear.In this study,we demonstrate that the posttranslational regulation of the Target of Rapamycin(TOR)kinase is a key determinant in maintaining this balance.Inhibiting TOR activity,either pharmacologically or genetically,enhanced root immunity and mitigated pathogen-induced root growth suppression.ToR inactivation preceded resource depletion during the early stage of infection,indicating an active resource reallocation mechanism that prioritizes defense activation over growth maintenance.Mechanistic studies uncovered a phosphorylation circuit where pathogen recognition activates the lectin receptor-like kinase LORE,which stimulates the phosphatase LOPP to directly dephosphorylate and inactivate TOR.Subsequently,LOPP is degraded via a proteasomal pathway,restoring TOR activity.This phosphorylation circuit enables plants to prioritize immune responses while maintaining growth flexibility.Our findings establish TOR as a key regulator of resource allocation during host-microbe interactions and offer a mechanistic framework for understanding growth-immunity trade-offs in plants.
