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Synthesis of Cationic Molybdenum Imido 2-Adamantylidene Complexes from Bispyrrolides via Cationic Pyrrolenine Complexes
Organometallics ( IF 2.8 ) Pub Date : 2021-08-20 , DOI: 10.1021/acs.organomet.1c00415 Bhaskar Paul 1 , Richard R. Schrock 1 , Charlene Tsay 1
Organometallics ( IF 2.8 ) Pub Date : 2021-08-20 , DOI: 10.1021/acs.organomet.1c00415 Bhaskar Paul 1 , Richard R. Schrock 1 , Charlene Tsay 1
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Mo(N-t-Bu)(Adene)(Me2Pyr)2 (2a) (Adene = 2-Adamantylidene, Me2Pyr = 2,5-dimethylpyrrolide) and Mo(NAr)(Adene)(Me2Pyr)2 (2b) (Ar = 2,6-diisopropylphenyl) were prepared through addition of LiMe2Pyr to Mo(N-t-Bu)(Adene)(Triflate)2(dme) and Mo(NAr)(Adene)(Triflate)2(dme) complexes, respectively. Addition of 1 equiv of [Me2PhNH][BArF4] (ArF = 3,5-(CF3)2C6H3) and more than 2 equiv of pivalonitrile to Mo(NC6F5)(Adene)(Me2Pyr)2, followed by 1 equiv of HMTOH (2,6-Mesityl2C6H3OH), led to isolation of yellow crystalline Mo(NC6F5)(Adene)(OHMT)(Piv)2(BArF4) (3, Piv = pivalonitrile). Reactions analogous to that for 3 were found to produce Mo(NC6F5)(Adene)[OC(CF3)3](Piv)2(BArF4) (4), Mo(NC6F5)(Adene)(OHMT)(PhF6CN)2(BArF4) (5; PhF6CN = 3,5-(CF3)2C6H3CN ), Mo(NAr)(Adene)(OHMT)(PhF6CN)2(BArF4) (6), Mo(NAr)(Adene)[OC(CF3)3](Piv)2(BArF4) (7), and Mo(N-t-Bu)(Adene)(OHMT)(PhF6CN)2(BArF4) (8). Compounds 3, 6, and 7 were found to have basically square pyramidal structures with trans nitriles in two basal positions. The bisnitrile complexes are active metathesis catalysts in the presence of 1 equiv of B(C6F5)3, consistent with the 14e monononitrile cationic complexes being the active species. The 14e complex required for metathesis is accessed most readily in bis PhF6CN complexes.
中文翻译：
通过阳离子吡咯啉配合物从双吡咯烷合成阳离子钼亚胺2-金刚烷基配合物
Mo(N- t- Bu)(Adene)(Me 2 Pyr) 2 ( 2a ) (Adene = 2-Adamantylidene, Me 2 Pyr = 2,5-二甲基吡咯烷) 和 Mo(NAr)(Adene)(Me 2 Pyr) 2 ( 2b ) (Ar = 2,6-二异丙基苯基) 通过将 LiMe 2 Pyr 添加到 Mo(N- t -Bu)(Adene)(Triflate) 2 (dme) 和 Mo(NAr)(Adene)(Triflate ) 2 (dme) 复合物。添加 1 当量的 [Me 2 PhNH][BAr F 4 ] (Ar F = 3,5-(CF 3 ) 2 C 6 H3 ) 和超过 2 当量的新戊腈到 Mo(NC 6 F 5 )(Adene)(Me 2 Pyr) 2，然后是 1 当量的 HMTOH（2,6-Mesityl 2 C 6 H 3 OH），导致分离黄色结晶 Mo(NC 6 F 5 )(Adene)(OHMT)(Piv) 2 (BAr F 4 ) ( 3 , Piv = 新戊腈)。发现类似于3 的反应生成 Mo(NC 6 F 5 )(Adene)[OC(CF 3 ) 3 ](Piv) 2 (BAr F 4) ( 4 ), Mo(NC 6 F 5 )(Adene)(OHMT)(Ph F6 CN) 2 (BAr F 4 ) ( 5 ; Ph F6 CN = 3,5-(CF 3 ) 2 C 6 H 3 CN ) , Mo(NAr)(Adene)(OHMT)(Ph F6 CN) 2 (BAr F 4 ) ( 6 ), Mo(NAr)(Adene)[OC(CF 3 ) 3 ](Piv) 2 (BAr F 4 ) ) ( 7 ), 和 Mo(N- t- Bu)(Adene)(OHMT)(Ph F6CN) 2 (BAr F 4 ) ( 8 )。化合物3，6，和7被发现有基本上四方锥体结构与反式两种基础位置腈。双腈配合物是在 1 当量 B(C 6 F 5 ) 3存在下的活性复分解催化剂，与作为活性物质的 14e 单腈阳离子配合物一致。复分解所需的 14e 复合物最容易在 bis Ph F6 CN 复合物中获得。
更新日期：2021-09-13
中文翻译：
通过阳离子吡咯啉配合物从双吡咯烷合成阳离子钼亚胺2-金刚烷基配合物
Mo(N- t- Bu)(Adene)(Me 2 Pyr) 2 ( 2a ) (Adene = 2-Adamantylidene, Me 2 Pyr = 2,5-二甲基吡咯烷) 和 Mo(NAr)(Adene)(Me 2 Pyr) 2 ( 2b ) (Ar = 2,6-二异丙基苯基) 通过将 LiMe 2 Pyr 添加到 Mo(N- t -Bu)(Adene)(Triflate) 2 (dme) 和 Mo(NAr)(Adene)(Triflate ) 2 (dme) 复合物。添加 1 当量的 [Me 2 PhNH][BAr F 4 ] (Ar F = 3,5-(CF 3 ) 2 C 6 H3 ) 和超过 2 当量的新戊腈到 Mo(NC 6 F 5 )(Adene)(Me 2 Pyr) 2，然后是 1 当量的 HMTOH（2,6-Mesityl 2 C 6 H 3 OH），导致分离黄色结晶 Mo(NC 6 F 5 )(Adene)(OHMT)(Piv) 2 (BAr F 4 ) ( 3 , Piv = 新戊腈)。发现类似于3 的反应生成 Mo(NC 6 F 5 )(Adene)[OC(CF 3 ) 3 ](Piv) 2 (BAr F 4) ( 4 ), Mo(NC 6 F 5 )(Adene)(OHMT)(Ph F6 CN) 2 (BAr F 4 ) ( 5 ; Ph F6 CN = 3,5-(CF 3 ) 2 C 6 H 3 CN ) , Mo(NAr)(Adene)(OHMT)(Ph F6 CN) 2 (BAr F 4 ) ( 6 ), Mo(NAr)(Adene)[OC(CF 3 ) 3 ](Piv) 2 (BAr F 4 ) ) ( 7 ), 和 Mo(N- t- Bu)(Adene)(OHMT)(Ph F6CN) 2 (BAr F 4 ) ( 8 )。化合物3，6，和7被发现有基本上四方锥体结构与反式两种基础位置腈。双腈配合物是在 1 当量 B(C 6 F 5 ) 3存在下的活性复分解催化剂，与作为活性物质的 14e 单腈阳离子配合物一致。复分解所需的 14e 复合物最容易在 bis Ph F6 CN 复合物中获得。
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