Homoleptic Tris-Diphosphine Re(I) and Re(II) Complexes and Re(II) Photophysics and Photochemistry
作者:Jeramie J. Adams、Navamoney Arulsamy、B. Patrick Sullivan、Dean M. Roddick、Amelia Neuberger、Russell H. Schmehl
DOI:10.1021/acs.inorgchem.5b01395
日期:2015.12.7
tris-homoleptic diphosphine complexes [(PP)3Re]+ (PP = 1,2-bis(dimethylphosphino)ethane (dmpe), 1,2-bis(diethylphosphino)ethane (depe), bis(dimethylphosphino)methane (dmpm), bis(diphenylphosphino)methane (dppm), Me2PCH2PPh2, 1,3-bis(dimethylphosphino)propane (dmpp), or 1,2-bis(dimethyl-phosphino)benzene (dmpb)) were achieved by single-pot reactions exploiting the reducing potential of the phosphines when
已证明[(dmpe)3 Re] 2+(dmpe = 1,2-双(二甲基膦基)乙烷)的配体到金属的电荷转移态(LMCT)是强氧化剂(E 0(Re 2+ * / Re +)= 2.61 V(相对于标准甘汞电极)。传统上,这种配合物是通过非平凡的路线以低收率制备的,而通过优化一般配合物[(PP)3 Re] 2+(PP =螯合二膦)的基态和发射能性质,却取得了很少的进展。膦改性。改进的Re(I)三亲二膦配合物[(PP)3 Re] +的合成(PP = 1,2-双(二甲基膦基)乙烷(dmpe),1,2-双(二乙基膦基)乙烷(depe),双(二甲基膦基)甲烷(dmpm),双(二苯基膦基)甲烷(dppm),Me 2 PCH 2 PPH 2,1,3-双(二甲基膦基)丙烷(DMPP),或1,2-双(二甲基膦基)苯(dmpb))通过单罐反应时与反应利用膦的还原电位达到1,2-二氯苯中的Re V氧配合物在160–180°C下。[(PP)3