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由超庞大的氢化三（吡唑基）硼酸配体支撑的氢化锶的反应活性。

Reactivity of Strontium Hydride Supported by the Superbulky Hydrotris(pyrazolyl)borate Ligand.

作者信息

Gong Xun, Shi Xianghui, Deng Peng, Cheng Jianhua

机构信息

State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, No. 5625 Renmin Street, Changchun 130022, China.

School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, Anhui 230026, China.

出版信息

Inorg Chem. 2024 Oct 28;63(43):20654-20663. doi: 10.1021/acs.inorgchem.4c03296. Epub 2024 Oct 18.

DOI:10.1021/acs.inorgchem.4c03296
PMID:39421973
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11523258/
Abstract

Hydrogenolysis of [(Tp)Sr{CH(SiMe)}] () (Tp = hydrotris(3-adamantyl-5-isopropyl-pyrazolyl)borate) in hexane solution under 20 atm of H allowed for the isolation of strontium hydride [(Tp)Sr(μ-H)] () in good yield. Complex exhibits the dimeric nature in solid state, featuring two different bond modes between the Sr center and Tp ligand. Treatment of complex with PhC(H)═NBu or PhCHBpin (Bpin = pinacolateborane) afforded the strontium amide complex [(Tp)Sr{N(CHPh)(Bu)}] () and hydroborate complex [(Tp)Sr{μ-HBpin(CHPh)}] (), respectively. Reactions of complex with 2-picoline, 2-phenylquinoline, or 2-phenylpyridine led to the formation of strontium 2-pyridylmethylene/2-picoline complex [(Tp)Sr(2-CH-Py)(2-picoline)] (), reductively coupling diphenyl-biquinolide complex [{(Tp)Sr}(2,2'-Ph-4,4'-dihydro-4,4'-biquinolide)] (), and diphenyl-bipyridyl radical complex [(Tp)Sr(6,6'-Ph-2,2'-bipyridyl)] (), separately. All of the complexes have been well characterized, including NMR spectrum and single-crystal X-ray analysis.

摘要

在20个大气压的氢气氛围下，[(Tp)Sr{CH(SiMe)}]（ ）（Tp = 氢化三(3-金刚烷基-5-异丙基-吡唑基)硼酸酯）在己烷溶液中发生氢解反应，以良好的产率分离得到氢化锶[(Tp)Sr(μ-H)]（ ）。配合物 在固态时呈现二聚体性质，其Sr中心与Tp配体之间具有两种不同的键合模式。用PhC(H)═NBu或PhCHBpin（Bpin = 频哪醇硼烷）处理配合物 ，分别得到锶酰胺配合物[(Tp)Sr{N(CHPh)(Bu)}]（ ）和硼氢化配合物[(Tp)Sr{μ-HBpin(CHPh)}]（ ）。配合物 与2-甲基吡啶、2-苯基喹啉或2-苯基吡啶反应，分别生成锶2-吡啶基亚甲基/2-甲基吡啶配合物[(Tp)Sr(2-CH-Py)(2-甲基吡啶)]（ ）、还原偶联二苯基-双喹诺内酯配合物[{(Tp)Sr}(2,2'-Ph-4,4'-二氢-4,4'-联喹诺内酯)]（ ）和二苯基-联吡啶自由基配合物[(Tp)Sr(6,6'-Ph-2,2'-联吡啶)]（ ）。所有配合物均已通过包括核磁共振谱和单晶X射线分析在内的方法进行了充分表征。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dfa2/11523258/b9c964f33398/ic4c03296_0012.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dfa2/11523258/b9c964f33398/ic4c03296_0012.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dfa2/11523258/f594959eadd6/ic4c03296_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dfa2/11523258/f3e12c33c5da/ic4c03296_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dfa2/11523258/ab7a0374845c/ic4c03296_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dfa2/11523258/ba3d1099e9c3/ic4c03296_0010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dfa2/11523258/77ead919b8b1/ic4c03296_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dfa2/11523258/541c3a3997e7/ic4c03296_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dfa2/11523258/432b3999179d/ic4c03296_0011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dfa2/11523258/d0dabb30a18c/ic4c03296_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dfa2/11523258/a40b3d3527e8/ic4c03296_0007.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dfa2/11523258/b9c964f33398/ic4c03296_0012.jpg

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