Prashanth Billa, Singh Sanjay
Department of Chemical Sciences, Indian Institute of Science Education and Research Mohali, Knowledge City, Sector 81, SAS Nagar, Mohali 140306, Punjab, India.
Dalton Trans. 2016 Apr 14;45(14):6079-87. doi: 10.1039/c5dt02287h. Epub 2015 Sep 30.
The influence of a sterically demanding iminophosphonamide ligand, [(2,6-iPr2C6H3N)P(Ph2)(NtBu)]H (LH), on the synthesis and stability of a heteroleptic germylene monochloride, [(2,6-iPr2C6H3N)P(Ph2)(NtBu)]GeCl (1), and its reaction chemistry has been discussed. Complex 1 behaves as a Lewis base to form an adduct with Fe(CO)4, namely [(2,6-iPr2C6H3N)P(Ph2)(NtBu)]Ge(Cl)Fe(CO)4 (2). Reaction of 1 with KOtBu or AgOSO2CF3 affords Ge(ii) compounds, [(2,6-iPr2C6H3N)P(Ph2)(NtBu)]GeR (R = OtBu (3), OSO2CF3 (4)). Treatment of complex 1 with elemental sulfur or selenium leads to heavier analogues of germaacid chlorides, [(2,6-iPr2C6H3N)P(Ph2)(NtBu)]Ge(E)Cl (E = S (5), Se (6)). Similarly, compound 3 on reaction with elemental sulfur or selenium produces heavier analogues of germaesters, [(2,6-iPr2C6H3N)P(Ph2)(NtBu)]Ge(E)OtBu (E = S (7), Se (8)). Complexes 1-8 were characterized using multinuclear NMR and EI-MS, and solid state structures of complexes 1-3, 5 and 8 have been elucidated using single crystal X-ray diffraction.
空间位阻较大的亚氨基膦酰胺配体[(2,6-二异丙基苯基)二苯基(叔丁基氨基)膦]氢（LH）对杂配型一氯化锗烯[(2,6-二异丙基苯基)二苯基(叔丁基氨基)膦]锗氯（1）的合成、稳定性及其反应化学的影响已被讨论。配合物1表现为路易斯碱，与Fe(CO)4形成加合物，即[(2,6-二异丙基苯基)二苯基(叔丁基氨基)膦]锗(氯)Fe(CO)4（2）。1与叔丁醇钾或三氟甲磺酸银反应得到锗（II）化合物[(2,6-二异丙基苯基)二苯基(叔丁基氨基)膦]锗R（R = 叔丁氧基（3），三氟甲磺酸根（4））。用元素硫或硒处理配合物1会生成锗酰氯的较重类似物[(2,6-二异丙基苯基)二苯基(叔丁基氨基)膦]锗（E）氯（E = S（5），Se（6））。类似地，化合物3与元素硫或硒反应会生成锗酸酯的较重类似物[(2,6-二异丙基苯基)二苯基(叔丁基氨基)膦]锗（E）叔丁氧基（E = S（7），Se（8））。配合物1 - 8通过多核NMR和EI-MS进行了表征，配合物1 - 3、5和8的固态结构通过单晶X射线衍射得以阐明。
