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Calcium formamidinate derivatives by hydride insertion of carbodiimides†
Dalton Transactions ( IF 3.5 ) Pub Date : 2019-02-26 00:00:00 , DOI: 10.1039/c8dt05107k Joshua Dyall 1, 2, 3, 4 , Michael S. Hill 1, 2, 3, 4 , Mary F. Mahon 1, 2, 3, 4 , Luke Teh 1, 2, 3, 4 , Andrew S. S. Wilson 1, 2, 3, 4
Dalton Transactions ( IF 3.5 ) Pub Date : 2019-02-26 00:00:00 , DOI: 10.1039/c8dt05107k Joshua Dyall 1, 2, 3, 4 , Michael S. Hill 1, 2, 3, 4 , Mary F. Mahon 1, 2, 3, 4 , Luke Teh 1, 2, 3, 4 , Andrew S. S. Wilson 1, 2, 3, 4
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The carbodiimides, Ar/RN![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
CNAr/R, (Ar = 2,6-di-isopropylphenyl (Dipp), 4-methylphenyl; R = tert-butyl, cyclohexyl, iso-propyl), react with the polar Ca–H bonds of the dimeric β-diketiminato calcium hydride, [(BDI)CaH]2 (BDI = HC{(Me)CN-2,6-i-Pr2C6H3}2), to provide a series of heteroleptic calcium formamidinate derivatives. While reactions with carbodiimides bearing more sterically demanding substituents (Dipp, t-Bu, Cy) are straightforward, and provide four-coordinate compounds, less bulky iso-propyl or 4-methylphenyl substitution results in the sequestration of a further equivalent of the carbodiimide and the isolation of a heteroleptic hydride-bridged dinuclear species. This latter observation is suggested to be a reflection of the robust dimeric constitution of the calcium hydride reagent and the reduced steric demands of the di-para-tolyl carbodiimide reagent.
中文翻译：
通过碳二亚胺的氢化物插入生成甲酰胺钙衍生物†
碳二亚胺Ar / RNC NAr / R（Ar = 2,6-二异丙基苯基（Dipp），4-甲基苯基； R =叔丁基，环己基，异丙基）与Ca-H极性键反应β-二酮亚胺基二氢化钙[（BDI）CaH] 2（BDI = HC {（Me）CN-2,6-i-Pr 2 C 6 H 3 } 2）的合成，以提供一系列杂合的甲酰胺酸钙衍生品。而与碳二亚胺的反应带有更严格的取代基（Dipp，t-Bu，Cy）是简单的，并且提供四配位化合物，较小的异丙基或4-甲基苯基取代导致螯合另一当量的碳二亚胺，并分离出杂合氢化物桥接的双核物质。建议后者的观察结果反映了氢化钙试剂的稳健二聚体结构和二对甲苯基碳二亚胺试剂的降低的空间需求。
更新日期：2019-02-26
CNAr/R, (Ar = 2,6-di-isopropylphenyl (Dipp), 4-methylphenyl; R = tert-butyl, cyclohexyl, iso-propyl), react with the polar Ca–H bonds of the dimeric β-diketiminato calcium hydride, [(BDI)CaH]2 (BDI = HC{(Me)CN-2,6-i-Pr2C6H3}2), to provide a series of heteroleptic calcium formamidinate derivatives. While reactions with carbodiimides bearing more sterically demanding substituents (Dipp, t-Bu, Cy) are straightforward, and provide four-coordinate compounds, less bulky iso-propyl or 4-methylphenyl substitution results in the sequestration of a further equivalent of the carbodiimide and the isolation of a heteroleptic hydride-bridged dinuclear species. This latter observation is suggested to be a reflection of the robust dimeric constitution of the calcium hydride reagent and the reduced steric demands of the di-para-tolyl carbodiimide reagent.
中文翻译：
通过碳二亚胺的氢化物插入生成甲酰胺钙衍生物†
碳二亚胺Ar / RN
C NAr / R（Ar = 2,6-二异丙基苯基（Dipp），4-甲基苯基； R =叔丁基，环己基，异丙基）与Ca-H极性键反应β-二酮亚胺基二氢化钙[（BDI）CaH] 2（BDI = HC {（Me）CN-2,6-i-Pr 2 C 6 H 3 } 2）的合成，以提供一系列杂合的甲酰胺酸钙衍生品。而与碳二亚胺的反应带有更严格的取代基（Dipp，t-Bu，Cy）是简单的，并且提供四配位化合物，较小的异丙基或4-甲基苯基取代导致螯合另一当量的碳二亚胺，并分离出杂合氢化物桥接的双核物质。建议后者的观察结果反映了氢化钙试剂的稳健二聚体结构和二对甲苯基碳二亚胺试剂的降低的空间需求。
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