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氢键在质子转移至κ,κ,κ-N(CHCHP Pr)连接的镍钳形配合物中的作用

Roles of Hydrogen Bonding in Proton Transfer to κ,κ,κ-N(CHCHP Pr)-Ligated Nickel Pincer Complexes.

作者信息

Wellala Nadeesha P N, Luebking John D, Krause Jeanette A, Guan Hairong

机构信息

Department of Chemistry, University of Cincinnati, 301 Clifton Court, Cincinnati, Ohio 45221-0172, United States.

出版信息

ACS Omega. 2018 May 31;3(5):4986-5001. doi: 10.1021/acsomega.8b00777. Epub 2018 May 8.

DOI:10.1021/acsomega.8b00777
PMID:30023906
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6045406/
Abstract

The nickel PNP pincer complex ( PNP)NiPh ( PNP = κ,κ,κ-N(CHCHP Pr)) was prepared by reacting ( PNP)NiBr with PhMgCl or deprotonating [( PNP)NiPh]Y ( PNP = κ,κ,κ-HN(CHCHP Pr); Y = Br, PF) with KO Bu. The byproducts of the PhMgCl reaction were identified as [( PNP)NiPh]Br and ( PNP')NiPh ( PNP' = κ,κ,κ-N(CH=CHP Pr)(CHCHP Pr)). The methyl analog ( PNP)NiMe was synthesized from the reaction of ( PNP)NiBr with MeLi, although it was contaminated with ( PNP')NiMe due to ligand oxidation. Protonation of ( PNP)NiX (X = Br, Ph, Me) with various acids, such as HCl, water, and MeOH, was studied in CD. Nitrogen protonation was shown to be the most favorable process, producing a cationic species [( PNP)NiX] with the NH moiety hydrogen-bonded to the conjugate base (i.e., Cl, HO, or MeO). Protonation of the Ni-C bond was observed at room temperature with ( PNP)NiMe, whereas at 70 °C with ( PNP)NiPh, both resulting in [( PNP)NiCl]Cl as the final product. Protonation of ( PNP)NiBr was complicated by site exchange between Br and the conjugate base and by the degradation of the pincer complexes. Indene, which lacks hydrogen-bonding capability, was unable to protonate ( PNP)NiPh and ( PNP)NiMe, despite being more acidic than water and MeOH. Neutral and cationic nickel pincer complexes involved in this study, including ( PNP')NiBr, ( PNP)NiPh, ( PNP')NiPh, ( PNP)NiMe, [( PNP)NiPh]Y (Y = Br, PF, BPh), [( PNP)NiPh][NiCl], [( PNP)NiMe]Y (Y = Cl, Br, BPh), [( PNP)NiBr]Br, and [( PNP)NiCl]Cl, were characterized by X-ray crystallography.

摘要

镍PNP钳形配合物(PNP)NiPh(PNP = κ,κ,κ-N(CHCHP Pr))是通过使(PNP)NiBr与PhMgCl反应或用KO Bu使[(PNP)NiPh]Y(PNP = κ,κ,κ-HN(CHCHP Pr);Y = Br, PF)去质子化而制备的。PhMgCl反应的副产物被鉴定为[(PNP)NiPh]Br和(PNP')NiPh(PNP' = κ,κ,κ-N(CH=CHP Pr)(CHCHP Pr))。甲基类似物(PNP)NiMe是由(PNP)NiBr与MeLi反应合成的，尽管由于配体氧化而被(PNP')NiMe污染。在CD中研究了用各种酸(如HCl、水和MeOH)对(PNP)NiX(X = Br、Ph、Me)进行质子化反应。结果表明，氮质子化是最有利的过程，生成阳离子物种[(PNP)NiX]，其中NH部分与共轭碱(即Cl、HO或MeO)形成氢键。在室温下观察到(PNP)NiMe对Ni-C键进行质子化，而在70°C下(PNP)NiPh对Ni-C键进行质子化，最终产物均为[(PNP)NiCl]Cl。(PNP)NiBr的质子化反应因Br与共轭碱之间的位点交换以及钳形配合物的降解而变得复杂。茚缺乏氢键能力，尽管其酸性比水和甲醇强，但仍无法使(PNP)NiPh和(PNP)NiMe质子化。本研究中涉及的中性和阳离子镍钳形配合物，包括(PNP')NiBr、(PNP)NiPh、(PNP')NiPh、(PNP)NiMe、[(PNP)NiPh]Y(Y = Br、PF、BPh)、[(PNP)NiPh][NiCl]、[(PNP)NiMe]Y(Y = Cl、Br、BPh)、[(PNP)NiBr]Br和[(PNP)NiCl]Cl，均通过X射线晶体学进行了表征。

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