A monoanionic nitrogen-phosphorus ligand(CH_(3))_(2)NCH_(2)CH_(2)NHPiPr_(2)(L_(3))was designed and the corresponding U(Ⅳ)chloride complex{[(CH_(3))_(2)NCH_(2)CH_(2)NPiPr_(2)]_(2)UCl_(2)}(1)and U(Ⅳ)iodide complex{[(C...A monoanionic nitrogen-phosphorus ligand(CH_(3))_(2)NCH_(2)CH_(2)NHPiPr_(2)(L_(3))was designed and the corresponding U(Ⅳ)chloride complex{[(CH_(3))_(2)NCH_(2)CH_(2)NPiPr_(2)]_(2)UCl_(2)}(1)and U(Ⅳ)iodide complex{[(CH_(3))_(2)NCH_(2)CH_(2)NPiPr_(2)]_(2)UI_(2)}(_(2))were readily synthesized.Complexes 1 and_(2)were fully characterized and the reactivity of complex 1 was further investigated.Complex_(3){[(CH_(3))_(2)NCH_(2)CH_(2)NPiPr_(2)]_(2)U(C1_(2)H_(8))}with a uranium cyclopentadiene unit was constructed by the reaction of 1 with 2,2’-dilithiobiphenyl,which is a rare example of a homoleptic metallafluorene containing an actinide element.展开更多
Bisphosphinoaryl ruthenium(Ⅱ) compounds are synthesized using two distinctsynthetic routes. One route, direct cycloruthenation, consists of the reaction of the parent arenecompound R-PCHP with [RuCl_2 (PPh_3)_3] in c...Bisphosphinoaryl ruthenium(Ⅱ) compounds are synthesized using two distinctsynthetic routes. One route, direct cycloruthenation, consists of the reaction of the parent arenecompound R-PCHP with [RuCl_2 (PPh_3)_3] in chlorinated solvents. However, this route suffers frommajor drawbacks because HCl is formed as well as free triphenylphoshine. The other route, thetranscyclometalation reaction, involves the interconversion of one cyclometalated ligand metalcomplex, [RuCl (NCN) (PPh_3)], into another complex, [RuCl (R-PCP) (PPh_3)], with concomitantconsumption and formation of the corresponding arenes R-PCHP and NCHN, respectively.展开更多
The Au and Ni monoanionic complexes of tert-butyl and diisopropyl substituted thiophenedithiolate ligands,[M(α-tb-tpdt)_(2)]and[M(α-dp-tpdt)_(2)],were synthesized and characterized namely by single crystal X-ray dif...The Au and Ni monoanionic complexes of tert-butyl and diisopropyl substituted thiophenedithiolate ligands,[M(α-tb-tpdt)_(2)]and[M(α-dp-tpdt)_(2)],were synthesized and characterized namely by single crystal X-ray diffraction and magnetic susceptibility measurements.These complexes,prepared in a first step as monoanionic species,are easier to oxidize than the related non-substituted thiophenedithiolates and could be obtained also as stable neutral species.As expected,the peripheral alkyl groups in the ligands also confer a high solubility to the complexes in common organic solvents.The neutral gold complex[Au(α-tb-tpdt)_(2)]presents a significant ligand asymmetry indicative of unpaired electron localization in one ligand at variance with[Au(α-dp-tpdt)_(2)]that is within experimental uncertainty fully symmetric illustrating the role of intermolecular interactions in the stabilization of SOMO⋯SOMO interactions.While in[Au(α-tb-tpdt)_(2)]a significant intermolecular interaction between paramagnetic molecules is possible leading to diamagnetic dimers of molecules,in[Au(α-dp-tpdt)_(2)]the bulkier substituents prevent the intermolecular interactions,leading to a regular stacking of molecules in symmetrical configuration.The regular stacks of paramagnetic[Au(α-dp-tpdt)2]units behave,at high temperatures,as antiferromagnetic chains undergoing an AFM transition at ca.25 K.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
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
基金supported by the National Key R&D Program of China(2021YFA1502500)the National Natural Science Foundation of China(No.91961116 and 22271138)+1 种基金the Natural Science Foundation of Jiangsu Province(BK20220065)Programs for High-Level Entrepreneurial and Innovative Talents Introduction of Jiangsu Province.
文摘A monoanionic nitrogen-phosphorus ligand(CH_(3))_(2)NCH_(2)CH_(2)NHPiPr_(2)(L_(3))was designed and the corresponding U(Ⅳ)chloride complex{[(CH_(3))_(2)NCH_(2)CH_(2)NPiPr_(2)]_(2)UCl_(2)}(1)and U(Ⅳ)iodide complex{[(CH_(3))_(2)NCH_(2)CH_(2)NPiPr_(2)]_(2)UI_(2)}(_(2))were readily synthesized.Complexes 1 and_(2)were fully characterized and the reactivity of complex 1 was further investigated.Complex_(3){[(CH_(3))_(2)NCH_(2)CH_(2)NPiPr_(2)]_(2)U(C1_(2)H_(8))}with a uranium cyclopentadiene unit was constructed by the reaction of 1 with 2,2’-dilithiobiphenyl,which is a rare example of a homoleptic metallafluorene containing an actinide element.
文摘Bisphosphinoaryl ruthenium(Ⅱ) compounds are synthesized using two distinctsynthetic routes. One route, direct cycloruthenation, consists of the reaction of the parent arenecompound R-PCHP with [RuCl_2 (PPh_3)_3] in chlorinated solvents. However, this route suffers frommajor drawbacks because HCl is formed as well as free triphenylphoshine. The other route, thetranscyclometalation reaction, involves the interconversion of one cyclometalated ligand metalcomplex, [RuCl (NCN) (PPh_3)], into another complex, [RuCl (R-PCP) (PPh_3)], with concomitantconsumption and formation of the corresponding arenes R-PCHP and NCHN, respectively.
基金supported by FCT(Portugal)through contracts UID/Multi/04349/2013,PTDC/QEQ-SUP/1413/2012 and RECI/QEQ-QIN/0189/2012doctoral grants to J.T.C.(SFRH/BD/84628/2012)R.A.L.S.(SFRH/BD/86131/2012).
文摘The Au and Ni monoanionic complexes of tert-butyl and diisopropyl substituted thiophenedithiolate ligands,[M(α-tb-tpdt)_(2)]and[M(α-dp-tpdt)_(2)],were synthesized and characterized namely by single crystal X-ray diffraction and magnetic susceptibility measurements.These complexes,prepared in a first step as monoanionic species,are easier to oxidize than the related non-substituted thiophenedithiolates and could be obtained also as stable neutral species.As expected,the peripheral alkyl groups in the ligands also confer a high solubility to the complexes in common organic solvents.The neutral gold complex[Au(α-tb-tpdt)_(2)]presents a significant ligand asymmetry indicative of unpaired electron localization in one ligand at variance with[Au(α-dp-tpdt)_(2)]that is within experimental uncertainty fully symmetric illustrating the role of intermolecular interactions in the stabilization of SOMO⋯SOMO interactions.While in[Au(α-tb-tpdt)_(2)]a significant intermolecular interaction between paramagnetic molecules is possible leading to diamagnetic dimers of molecules,in[Au(α-dp-tpdt)_(2)]the bulkier substituents prevent the intermolecular interactions,leading to a regular stacking of molecules in symmetrical configuration.The regular stacks of paramagnetic[Au(α-dp-tpdt)2]units behave,at high temperatures,as antiferromagnetic chains undergoing an AFM transition at ca.25 K.
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.
