Insertion of fluorenone into the lanthanum–phosphorus bond of terminal phosphido complexes(PN)2La(PHR)(R=Mes(1a),R=Ph(1b)and R=tBu(1c))results in the formation of light-sensitive hemiphosphinal complexes 2a–c.Upon e...Insertion of fluorenone into the lanthanum–phosphorus bond of terminal phosphido complexes(PN)2La(PHR)(R=Mes(1a),R=Ph(1b)and R=tBu(1c))results in the formation of light-sensitive hemiphosphinal complexes 2a–c.Upon exposure to daylight,the P–C bonds in 2a–c break resulting in the formation of diphospines and a lanthanum bound fluorenonyl-radical.The scope and mechansim of this reaction are experimentally and theoretically evaluated.展开更多
The oxidative coupling of nitride ligands(N3−)to dinitrogen and its microscopic reverse,N_(2)-splitting to nitrides,are important elementary steps in chemical transformations,such as selective ammonia oxidation or nit...The oxidative coupling of nitride ligands(N3−)to dinitrogen and its microscopic reverse,N_(2)-splitting to nitrides,are important elementary steps in chemical transformations,such as selective ammonia oxidation or nitrogen fixation.Here an experimental and computational evaluation is provided for the homo-and heterocoupling of our previously reported iridium(IV)and iridium(V)nitrides[IrN(PNP)]^(n)(n=0,+1;PNP=N(CHCHPtBu_(2))_(2)).All three formal coupling products[(PNP)IrN_(2)Ir(PNP)]^(n)(n=0–+2)were structurally characterized.While the three coupling reactions are all thermodynamically feasible,homocoupling of[IrN(PNP)]+is kinetically hindered.The contributing parameters to relative coupling rates are discussed providing qualitative guidelines for the stability of electron rich transition metal nitrides.展开更多
文摘Insertion of fluorenone into the lanthanum–phosphorus bond of terminal phosphido complexes(PN)2La(PHR)(R=Mes(1a),R=Ph(1b)and R=tBu(1c))results in the formation of light-sensitive hemiphosphinal complexes 2a–c.Upon exposure to daylight,the P–C bonds in 2a–c break resulting in the formation of diphospines and a lanthanum bound fluorenonyl-radical.The scope and mechansim of this reaction are experimentally and theoretically evaluated.
基金the European Research Council(Grant Agreement 646747)for generous support。
文摘The oxidative coupling of nitride ligands(N3−)to dinitrogen and its microscopic reverse,N_(2)-splitting to nitrides,are important elementary steps in chemical transformations,such as selective ammonia oxidation or nitrogen fixation.Here an experimental and computational evaluation is provided for the homo-and heterocoupling of our previously reported iridium(IV)and iridium(V)nitrides[IrN(PNP)]^(n)(n=0,+1;PNP=N(CHCHPtBu_(2))_(2)).All three formal coupling products[(PNP)IrN_(2)Ir(PNP)]^(n)(n=0–+2)were structurally characterized.While the three coupling reactions are all thermodynamically feasible,homocoupling of[IrN(PNP)]+is kinetically hindered.The contributing parameters to relative coupling rates are discussed providing qualitative guidelines for the stability of electron rich transition metal nitrides.
