Geitner Felix S, Klein Wilhelm, Fässler Thomas F
Department Chemie, Technische Universität München, Lichtenbergstraße 4, 85747, Garching b. München, Germany.
WACKER Institute for Silicon Chemistry, Germany.
Angew Chem Int Ed Engl. 2018 Oct 26;57(44):14509-14513. doi: 10.1002/anie.201803476. Epub 2018 Aug 6.
Herein we report on the synthesis of the first multiple phosphine-substituted nonagermanide clusters in a one-step reaction from K Ge . Their reactions towards various transition metal complexes show a large variety of reactive sites. The novel threefold phosphine-functionalized [Ge ] clusters [Ge {PRR } ] {R: N Pr ; R : N Pr (1 a) or Bu (2 a)} are obtained by reaction of pristine [Ge ] clusters with the respective chlorophosphines. Subsequent reactions with NHC CuCl yield neutral compounds (NHC Cu)[Ge {P(N Pr ) } ] (3) and (NHC Cu)[Ge {P(N Pr ) Bu} ] (4), respectively. The reaction of neutral compound 3 with Cr(CO) (thf) yields the first uncharged fivefold substituted [Ge ] cluster (NHC Cu) [Ge {P(N Pr ) } Cr(CO) ] (5) via a ligand exchange reaction at the [Ge ] cluster core. Compounds 3 and 5 are characterized by single crystal structure determination.
在此，我们报道了由K₄Ge₉通过一步反应合成首个多膦取代的九锗簇合物。它们与各种过渡金属配合物的反应显示出多种多样的反应位点。通过原始的[Ge₉]簇合物与相应的氯膦反应，得到了新型的三重膦官能化的[Ge₉]簇合物[Ge₉{P(NPr₂)₂}₃]（R：NPr₂；R′：NPr₂（1a）或t-Bu（2a））。随后与NHC CuCl反应分别生成中性化合物（NHC Cu）[Ge₉{P(NPr₂)₂}₃]（3）和（NHC Cu）[Ge₉{P(NPr₂)₂t-Bu}]（4）。中性化合物3与Cr(CO)₆(thf)反应，通过在[Ge₉]簇合物核心发生配体交换反应，生成了首个不带电荷的五重取代的[Ge₉]簇合物（NHC Cu）₂[Ge₉{P(NPr₂)₂}₃Cr(CO)₃]（5）。化合物3和5通过单晶结构测定进行了表征。
