On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates.
On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates.
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DOI：
10.1002/chem.201603135
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发表时间：
2016-10-24
影响因子：
4.3
通讯作者：
Goicoechea, Jose M.
中科院分区：
文献类型：
--
作者：
Robinson, Thomas P.;Lo, Siu-Kwan;De Rosa, Daniel;Aldridge, Simon;Goicoechea, Jose M.
探讨了具有N，N-双（3，5-二叔丁基-2-苯酚）酰胺钳形配体（ONO 3-）的几何约束的第15族配合物的两亲性。尽管它们对具有极化元素-氢键的亲核底物的反应性不同（例如，NH3），磷（III）P（ONO）（1a）和砷（III）As（ONO）（1 B）化合物对带电亲核试剂和亲电子试剂表现出相似的反应性。1 a和1 B与KOtBu或KNPh 2反应得到阴离子配合物，其中亲核阴离子与磷属元素中心缔合（[（tBuO）Pn（ONO）]−（Pn=P（2 a），As（2 B））和[（Ph 2N）Pn（ONO）]−（Pn=P（3 a），As（3 B））。化合物2a随后可以与质子源或苄基溴反应，分别得到磷（V）化合物（tBuO）HP（ONO）（4a）和（tBuO）BzP（ONO）（5a），而类似的砷（V）化合物是不可获得的。亲电底物，如HOTf和MeOTf，优先与1a和1 B的配体骨架的氮原子缔合，产生阳离子物质，其可以被合理化为铵盐或胺稳定的膦或砷络合物（[Pn{ON（H）O}]+（Pn=P（6 a），As（6 B））和[Pn{ON（Me）O}]+（Pn=P（7 a），As（7 B））。1 a与带有亲核抗衡阴离子的酸（如HCl）反应生成磷（V）化合物HPCl（ONO）（8 a），而与1 B的类似反应导致HCl加成到As−O键之一上，得到ClAs{（H）ONO}（8 B）。通过7 a/7 B与KOtBu的反应，也可以在氮族元素中心和配体骨架上进行官能化，得到中性物质（tBuO）Pn{ON（Me）O}（Pn=P（9 a），As（9 B））。这些几何约束的复合物的两亲性反应性允许对Ia对小分子（如氨和水）的反应性机制有一些了解。
The ambiphilic nature of geometrically constrained Group 15 complexes bearing the N,N‐bis(3,5‐di‐tert‐butyl‐2‐phenolate)amide pincer ligand (ONO3−) is explored. Despite their differing reactivity towards nucleophilic substrates with polarised element–hydrogen bonds (e.g., NH3), both the phosphorus(III), P(ONO) (1 a), and arsenic(III), As(ONO) (1 b), compounds exhibit similar reactivity towards charged nucleophiles and electrophiles. Reactions of 1 a and 1 b with KOtBu or KNPh2 afford anionic complexes in which the nucleophilic anion associates with the pnictogen centre ([(tBuO)Pn(ONO)]− (Pn=P (2 a), As (2 b)) and [(Ph2N)Pn(ONO)]− (Pn=P (3 a), As (3 b)). Compound 2 a can subsequently be reacted with a proton source or benzylbromide to afford the phosphorus(V) compounds (tBuO)HP(ONO) (4 a) and (tBuO)BzP(ONO) (5 a), respectively, whereas analogous arsenic(V) compounds are inaccessible. Electrophilic substrates, such as HOTf and MeOTf, preferentially associate with the nitrogen atom of the ligand backbone of both 1 a and 1 b, giving rise to cationic species that can be rationalised as either ammonium salts or as amine‐stabilised phosphenium or arsenium complexes ([Pn{ON(H)O}]+ (Pn=P (6 a), As (6 b)) and [Pn{ON(Me)O}]+ (Pn=P (7 a), As (7 b)). Reaction of 1 a with an acid bearing a nucleophilic counteranion (such as HCl) gives rise to a phosphorus(V) compound HPCl(ONO) (8 a), whereas the analogous reaction with 1 b results in the addition of HCl across one of the As−O bonds to afford ClAs{(H)ONO} (8 b). Functionalisation at both the pnictogen centre and the ligand backbone is also possible by reaction of 7 a/7 b with KOtBu, which affords the neutral species (tBuO)Pn{ON(Me)O} (Pn=P (9 a), As (9 b)). The ambiphilic reactivity of these geometrically constrained complexes allows some insight into the mechanism of reactivity of 1 a towards small molecules, such as ammonia and water.
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影响因子：
15
作者：
Cui, Jingjing;Li, Yongxin;Kinjo, Rei
通讯作者：
Kinjo, Rei
影响因子：
2.3
作者：
Bezombes, JP;Carre, F;Reye, C
通讯作者：
Reye, C
影响因子：
6.1
作者：
COSIER, J;GLAZER, AM
通讯作者：
GLAZER, AM
影响因子：
16.6
作者：
Chase, Preston A.;Welch, Gregory C.;Stephan, Douglas W.
通讯作者：
Stephan, Douglas W.
影响因子：
4.3
作者：
Cui, Jingjing;Li, Yongxin;Kinjo, Rei
通讯作者：
Kinjo, Rei