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Formation and reactions of the 1, 8-naphthyridine (napy) ligated geminally dimetallated phenyl complexes [(napy)Cu2(Ph)]+, [(napy)Ag2(Ph)]+ and [(napy)CuAg(Ph)]+
European Journal of Mass Spectrometry ( IF 1.3 ) Pub Date : 2019-02-01 , DOI: 10.1177/1469066718795959
Qiuyan Jin 1 , Jiaye Li 1 , Alireza Ariafard 2 , Allan J Canty 3 , Richard Aj O'Hair 1
Affiliation  

Gas-phase ion trap mass spectrometry experiments and density functional theory calculations have been used to examine the routes to the formation of the 1,8-naphthyridine (napy) ligated geminally dimetallated phenyl complexes [(napy)Cu2(Ph)]+, [(napy)Ag2(Ph)]+ and [(napy)CuAg(Ph)]+ via extrusion of CO2 or SO2 under collision-induced dissociation conditions from their corresponding precursor complexes [(napy)Cu2(O2CPh)]+, [(napy)Ag2(O2CPh)]+, [(napy)CuAg(O2CPh)]+ and [(napy)Cu2(O2SPh)]+, [(napy)Ag2(O2SPh)]+, [(napy)CuAg(O2SPh)]+. Desulfination was found to be more facile than decarboxylation. Density functional theory calculations reveal that extrusion proceeds via two transition states: TS1 enables isomerization of the O,O-bridged benzoate to its O-bound form; TS2 involves extrusion of CO2 or SO2 with the concomitant formation of the organometallic cation and has the highest barrier. Of all the organometallic cations, only [(napy)Cu2(Ph)]+ reacts with water via hydrolysis to give [(napy)Cu2(OH)]+, consistent with density functional theory calculations which show that hydrolysis proceeds via the initial formation of the adduct [(napy)Cu2(Ph)(H2O)]+ which then proceeds via TS3 in which the coordinated H2O is deprotonated by the coordinated phenyl anion to give the product complex [(napy)Cu2(OH)(C6H6)]+, which then loses benzene.

中文翻译:

1, 8-萘啶 (napy) 连接的双金属化苯基络合物 [(napy)Cu2(Ph)]+、[(napy)Ag2(Ph)]+ 和 [(napy)CuAg(Ph)]+ 的形成和反应

气相离子阱质谱实验和密度泛函理论计算已被用于检查形成 1,8-萘啶 (napy) 连接的双金属化苯基络合物 [(napy)Cu2(Ph)]+, [ (napy)Ag2(Ph)]+ 和 [(napy)CuAg(Ph)]+ 通过在碰撞诱导解离条件下从其相应的前体复合物 [(napy)Cu2(O2CPh)]+、[( napy)Ag2(O2CPh)]+、[(napy)CuAg(O2CPh)]+ 和 [(napy)Cu2(O2SPh)]+、[(napy)Ag2(O2SPh)]+、[(napy)CuAg(O2SPh) ]+。发现脱硫比脱羧更容易。密度泛函理论计算表明,挤出通过两个过渡态进行:TS1 使 O,O 桥联苯甲酸酯异构化为其 O 键合形式;TS2 包括 CO2 或 SO2 的挤出以及有机金属阳离子的伴随形成,并且具有最高的阻隔性。在所有有机金属阳离子中,只有 [(napy)Cu2(Ph)]+ 通过水解与水反应生成 [(napy)Cu2(OH)]+,这与密度泛函理论计算一致,该计算表明水解通过初始形成进行加合物 [(napy)Cu2(Ph)(H2O)]+ 然后通过 TS3 进行,其中配位的 H2O 被配位的苯基阴离子去质子化,得到产物复合物 [(napy)Cu2(OH)(C6H6)] +,然后失去苯。
更新日期:2019-02-01
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