The direct construction of functionalized diphosphine ligands from P_(4)is a highly valuable but challenging transformation.In this work,a simple method has been developed for the direct formation of an amidofunctiona...The direct construction of functionalized diphosphine ligands from P_(4)is a highly valuable but challenging transformation.In this work,a simple method has been developed for the direct formation of an amidofunctionalized diphosphanato ligand from a silyl-bridged amido/methylene yttrium complex and white phosphorus.The resulting amido-functionalized diphosphanato yttrium complex 2 has proved to be a useful intermediate for further diversification of the diphosphine ligand through the metal template procedure,for which no evident limitations are enforced by initially present substituents and ancillary ligands,and some unprecedented reactivity patterns of the RPPR unit are revealed.The results described here demonstrate that appending a strongly coordinative substituent to the alkyl ligand together with a coordination to rare earth ions is an efficient strategy for controlling the cleavage modes of P_(4)during alkylation and the reactivity of the resulting diphosphanato complex.展开更多
The treatment of rare-earth metal dialkyl complexes Tp^(Me2)YBn_(2)(THF)(Bn=CH_(2)Ph,1^(Y))with P4 in toluene at ambient temperature formed yttrium norbornane-BnP_(7)^(4-)(2^(Y))and chain Bn_(4)P_(6)^(4-)(3^(Y))comple...The treatment of rare-earth metal dialkyl complexes Tp^(Me2)YBn_(2)(THF)(Bn=CH_(2)Ph,1^(Y))with P4 in toluene at ambient temperature formed yttrium norbornane-BnP_(7)^(4-)(2^(Y))and chain Bn_(4)P_(6)^(4-)(3^(Y))complexes,accompanied by the formation of PBn_(3)(I).However,only lutetium norbornane-BnP_(7)^(4-)complex 2^(Lu) and I were obtained from the reaction of 1^(Lu) with P_(4) under the same conditions.Moreover,an atom-economic conversion of P_(4) to PBn_(3) and norbornane-BnP_(7)(Me_(3)Si)_(4)(Ⅱ)was also realized by the treatment of Tp^(Me2)LuCl_(2)(THF)with KBn,followed by a sequential reaction with P_(4) and Me_(3)SiCl.These results indicated that P_(4) functionalization using rare-earth dialkyl complexes can form not only novel rare-earth polyphosphorus complexes,but also organophosphorus compounds.All new compounds have been characterized by NMR spectroscopy and single-crystal X-ray diffraction studies.展开更多
基金National Natural Science Foundation of China(grant no.21871058,22271051,and 22371049)973 program(2015CB856600)。
文摘The direct construction of functionalized diphosphine ligands from P_(4)is a highly valuable but challenging transformation.In this work,a simple method has been developed for the direct formation of an amidofunctionalized diphosphanato ligand from a silyl-bridged amido/methylene yttrium complex and white phosphorus.The resulting amido-functionalized diphosphanato yttrium complex 2 has proved to be a useful intermediate for further diversification of the diphosphine ligand through the metal template procedure,for which no evident limitations are enforced by initially present substituents and ancillary ligands,and some unprecedented reactivity patterns of the RPPR unit are revealed.The results described here demonstrate that appending a strongly coordinative substituent to the alkyl ligand together with a coordination to rare earth ions is an efficient strategy for controlling the cleavage modes of P_(4)during alkylation and the reactivity of the resulting diphosphanato complex.
基金the National Natural Science Foundation of China(Grant No.21472020,21732007,21871058,22371049)for financial support.
文摘The treatment of rare-earth metal dialkyl complexes Tp^(Me2)YBn_(2)(THF)(Bn=CH_(2)Ph,1^(Y))with P4 in toluene at ambient temperature formed yttrium norbornane-BnP_(7)^(4-)(2^(Y))and chain Bn_(4)P_(6)^(4-)(3^(Y))complexes,accompanied by the formation of PBn_(3)(I).However,only lutetium norbornane-BnP_(7)^(4-)complex 2^(Lu) and I were obtained from the reaction of 1^(Lu) with P_(4) under the same conditions.Moreover,an atom-economic conversion of P_(4) to PBn_(3) and norbornane-BnP_(7)(Me_(3)Si)_(4)(Ⅱ)was also realized by the treatment of Tp^(Me2)LuCl_(2)(THF)with KBn,followed by a sequential reaction with P_(4) and Me_(3)SiCl.These results indicated that P_(4) functionalization using rare-earth dialkyl complexes can form not only novel rare-earth polyphosphorus complexes,but also organophosphorus compounds.All new compounds have been characterized by NMR spectroscopy and single-crystal X-ray diffraction studies.
