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Fe and Co Complexes of Rigidly Planar Phosphino-Quinoline-Pyridine Ligands for Catalytic Hydrosilylation and Dehydrogenative Silylation
Organometallics ( IF 2.5 ) Pub Date : 2018-08-03 , DOI: 10.1021/acs.organomet.8b00416 Debashis Basu 1 , Ryan Gilbert-Wilson 1 , Danielle L. Gray 1 , Thomas B. Rauchfuss 1 , Aswini K. Dash 2
Organometallics ( IF 2.5 ) Pub Date : 2018-08-03 , DOI: 10.1021/acs.organomet.8b00416 Debashis Basu 1 , Ryan Gilbert-Wilson 1 , Danielle L. Gray 1 , Thomas B. Rauchfuss 1 , Aswini K. Dash 2
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Co and Fe dihalide complexes of a new rigidly planar PNN ligand platform are prepared and examined as precatalysts for hydrosilylation of alkenes. Lithiation of Thummel’s 8-bromo-2-(pyrid-2′-yl)quinoline followed by treatment with (i-Pr)2PCl and (C6F5)2PCl afforded the phosphine-quinoline-pyridine ligands, abbreviated RPQpy for R = i-Pr and C6F5, respectively. These ligands form 1:1 adducts with the dichlorides and dibromides of iron and cobalt. Crystallographic characterization of FeBr2(iPrPQpy), FeBr2(ArFPQpy), CoCl2(iPrPQpy), CoBr2(iPrPQpy), and CoCl2(ArFPQpy) confirmed that the M–P–C–C–N–C–C–N portion of these complexes is planar within 0.078 Å unlike previous generations of PNN complexes where deviations from planarity were ∼0.35 Å. Bond distances as well as magnetism indicate that the Fe complexes are high spin and the cobalt complexes are high spin or participate in spin equilibria. Also investigated were the NNN analogues of the RPQpy ligands, wherein the phosphine group was replaced by the mesityl ketimine. The complexes FeBr2(MesNQpy) and CoCl2(MesNQpy) were characterized crystallographically. Reduction of MX2(RPQpy) complexes with NaBHEt3 generates catalysts active for anti-Markovnikov silylation of simple and complex 1-alkenes with a variety of hydrosilanes. Catalysts derived from MesNQpy exhibited low activity. Fe-RPQpy derived catalysts favor hydrosilylation, whereas Co-RPQpy based catalysts favor dehydrogenative silylation. Catalysts derived from CoX2(iPrPQpy) convert hydrosilanes and ethylene to vinylsilanes. Related experiments were conducted on propylene to give propenylsilanes.
中文翻译：
刚性平面膦-喹啉-吡啶配体的铁和钴配合物催化氢化硅烷化和脱氢硅烷化
制备了一种新的刚性平面PNN配体平台的Co和Fe二卤化物配合物，并将其作为烯烃氢化硅烷化的预催化剂。将Thummel的8-溴-2-（吡啶-2'-基）喹啉锂化，然后用（i- Pr）2 PCl和（C 6 F 5）2 PCl处理，得到膦-喹啉-吡啶配体，缩写为R PQpy对于R ＝i- Pr和C 6 F 5。这些配体与铁和钴的二氯化物和二溴化物形成1：1加合物。FeBr 2（iPr PQpy），FeBr 2（ArFPQpy），CoCl 2（iPr PQpy），CoBr 2（iPr PQpy）和CoCl 2（ArF PQpy）证实这些配合物的M–P–C–C–N–C–C–N部分在0.078范围内为平面不同于前几代的PNN配合物，其平面度偏差约为0.35。键距和磁性表明Fe络合物为高自旋，而钴络合物为高自旋或参与自旋平衡。还研究了R PQpy配体的NNN类似物，其中膦基被异丁烯酮取代。FeBr 2（Mes NQpy）和CoCl 2（MesNQpy）在结晶学上被表征。用NaBHEt 3还原MX 2（R PQpy）配合物可生成催化剂，可用于简单和复杂的1-烯烃与多种氢硅烷的抗Markovnikov甲硅烷基化反应。源自Mes NQpy的催化剂表现出较低的活性。由Fe- R PQpy衍生的催化剂有利于氢化硅烷化，而基于Co- R PQpy的催化剂有利于脱氢甲硅烷基化。衍生自CoX 2（iPr PQpy）的催化剂将氢化硅烷和乙烯转化为乙烯基硅烷。在丙烯上进行了相关实验，得到丙烯基硅烷。
更新日期：2018-08-03
中文翻译：
刚性平面膦-喹啉-吡啶配体的铁和钴配合物催化氢化硅烷化和脱氢硅烷化
制备了一种新的刚性平面PNN配体平台的Co和Fe二卤化物配合物，并将其作为烯烃氢化硅烷化的预催化剂。将Thummel的8-溴-2-（吡啶-2'-基）喹啉锂化，然后用（i- Pr）2 PCl和（C 6 F 5）2 PCl处理，得到膦-喹啉-吡啶配体，缩写为R PQpy对于R ＝i- Pr和C 6 F 5。这些配体与铁和钴的二氯化物和二溴化物形成1：1加合物。FeBr 2（iPr PQpy），FeBr 2（ArFPQpy），CoCl 2（iPr PQpy），CoBr 2（iPr PQpy）和CoCl 2（ArF PQpy）证实这些配合物的M–P–C–C–N–C–C–N部分在0.078范围内为平面不同于前几代的PNN配合物，其平面度偏差约为0.35。键距和磁性表明Fe络合物为高自旋，而钴络合物为高自旋或参与自旋平衡。还研究了R PQpy配体的NNN类似物，其中膦基被异丁烯酮取代。FeBr 2（Mes NQpy）和CoCl 2（MesNQpy）在结晶学上被表征。用NaBHEt 3还原MX 2（R PQpy）配合物可生成催化剂，可用于简单和复杂的1-烯烃与多种氢硅烷的抗Markovnikov甲硅烷基化反应。源自Mes NQpy的催化剂表现出较低的活性。由Fe- R PQpy衍生的催化剂有利于氢化硅烷化，而基于Co- R PQpy的催化剂有利于脱氢甲硅烷基化。衍生自CoX 2（iPr PQpy）的催化剂将氢化硅烷和乙烯转化为乙烯基硅烷。在丙烯上进行了相关实验，得到丙烯基硅烷。
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