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Generation of Annelated Dicarbenes and Their Alkali-Metal Chelate Complexes in Solution: Equilibrium between Hetero- and Homoleptic NHC Lithium Complexes
Organometallics ( IF 2.5 ) Pub Date : 2018-03-07 00:00:00 , DOI: 10.1021/acs.organomet.8b00053 Kim S. Flaig 1 , Benjamin Raible 1 , Verena Mormul 1 , Natalie Denninger 1 , Cäcilia Maichle-Mössmer 1 , Doris Kunz 1
Organometallics ( IF 2.5 ) Pub Date : 2018-03-07 00:00:00 , DOI: 10.1021/acs.organomet.8b00053 Kim S. Flaig 1 , Benjamin Raible 1 , Verena Mormul 1 , Natalie Denninger 1 , Cäcilia Maichle-Mössmer 1 , Doris Kunz 1
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Attempts to generate the free bis(N-heterocyclic carbene) vegiR (R = nPr, tBu; vegiR = 2,7-dihydro-2,7-dialkyldiimidazo[1,5-b:5′,1′-f]pyridazine-1,8-diylidene) from its imidazolium salts 1 with alkali-metal bases resulted exclusively in the formation of the respective lithium, sodium, and potassium complexes 2–4 due to the strongly chelating properties of the dicarbene. DFT calculations reveal pronounced dispersion interactions in the case of N-tert-butyl substituents as the reason for the formation of the homoleptic lithium species 2b-H in solution. The dynamic behavior of the lithium complexes in equilibrium was studied by NMR techniques. Attempts to liberate the free carbenes by addition of the respective crown ethers failed for the lithium and sodium complexes. Deprotonation of the imidazolium salts 1a,b with the strong metal-free phosphazene base P4-tBu ({(Me2N)3PN}3PNtBu) generated successfully the free dicarbenes vegiR (5) and monocarbene 6b in solution.
中文翻译：
溶液中生成的双碳酸二苯酯及其碱金属螯合物的生成：杂合和均质NHC锂复合物之间的平衡
尝试生成游离的双（N-杂环卡宾）vegi R（R = n Pr，t Bu; vegi R = 2,7-二氢-2,7-二烷基二咪唑[1,5- b：5'，1'- ˚F从其咪唑盐]哒嗪-1,8-二亚基）1与碱金属碱在相应的锂，钠，和钾复合物的形成导致只2 - 4由于dicarbene的强螯合性质。DFT计算表明，在N-叔丁基取代基的情况下，明显的分散相互作用是形成均配锂物质2b-H的原因在解决方案中。通过核磁共振技术研究了锂配合物在平衡状态下的动力学行为。通过添加相应的冠醚来释放游离的卡宾的尝试对于锂和钠络合物而言是失败的。的咪唑鎓盐的脱质子化1a中，b与强无金属的磷腈碱P 4吨卜（{（ME 2 N）3 PN} 3 PN吨成功生成卜）的游离dicarbenes VEGI - [R （5）和monocarbene 6B在溶液中。
更新日期：2018-03-08
中文翻译：
溶液中生成的双碳酸二苯酯及其碱金属螯合物的生成：杂合和均质NHC锂复合物之间的平衡
尝试生成游离的双（N-杂环卡宾）vegi R（R = n Pr，t Bu; vegi R = 2,7-二氢-2,7-二烷基二咪唑[1,5- b：5'，1'- ˚F从其咪唑盐]哒嗪-1,8-二亚基）1与碱金属碱在相应的锂，钠，和钾复合物的形成导致只2 - 4由于dicarbene的强螯合性质。DFT计算表明，在N-叔丁基取代基的情况下，明显的分散相互作用是形成均配锂物质2b-H的原因在解决方案中。通过核磁共振技术研究了锂配合物在平衡状态下的动力学行为。通过添加相应的冠醚来释放游离的卡宾的尝试对于锂和钠络合物而言是失败的。的咪唑鎓盐的脱质子化1a中，b与强无金属的磷腈碱P 4吨卜（{（ME 2 N）3 PN} 3 PN吨成功生成卜）的游离dicarbenes VEGI - [R （5）和monocarbene 6B在溶液中。
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