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使用三吡唑基硼酸铑配合物对烷基氰化物进行活化。

The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex.

作者信息

Vetter Andrew J, Rieth Ryan D, Jones William D

机构信息

Department of Chemistry, University of Rochester, Rochester, NY 14627, USA.

出版信息

Proc Natl Acad Sci U S A. 2007 Apr 24;104(17):6957-62. doi: 10.1073/pnas.0609726104. Epub 2007 Mar 23.

DOI:10.1073/pnas.0609726104
PMID:17384154
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC1855398/
Abstract

The photochemical reaction of Tp'Rh(L)(eta2-PhN=L) [Tp' = tris-(3,5-dimethyl pyrazolyl)borate, L = CNCH(2)CMe(3)] to form the coordinatively unsaturated reactive fragment, [Tp'Rh(L)], in the presence of alkylnitriles has been studied. The [Tp'Rh(L)] complex has been shown to selectively activate the primary C H terminus of acetonitrile, propionitrile, butyronitrile, and valeronitrile. The resulting hydrides showed uncharacteristic stability in the presence of C(6)D(6) and their rates of reductive elimination were monitored by (1)H NMR spectroscopy. Competition reactions permit the establishment of the relative stabilities of the activation products.

摘要

研究了 Tp'Rh(L)(η²-PhN=L) [Tp' = 三(3,5-二甲基吡唑基)硼酸酯，L = CNCH(2)CMe(3)] 在烷基腈存在下发生光化学反应形成配位不饱和反应性片段 [Tp'Rh(L)] 的过程。已证明 [Tp'Rh(L)] 配合物可选择性地活化乙腈、丙腈、丁腈和戊腈的一级 C-H 端基。所得氢化物在 C(6)D(6) 存在下表现出异常的稳定性，其还原消除速率通过¹H NMR 光谱进行监测。竞争反应有助于确定活化产物的相对稳定性。

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J Am Chem Soc. 2005 Sep 7;127(35):12315-22. doi: 10.1021/ja042152q.
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Sterically directed functionalization of aromatic C-H bonds: selective borylation ortho to cyano groups in arenes and heterocycles.芳族C-H键的空间定向官能团化：芳烃和杂环中氰基邻位的选择性硼化。
J Am Chem Soc. 2005 Aug 3;127(30):10539-44. doi: 10.1021/ja0428309.
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Kinetics, thermodynamics, and effect of BPh3 on competitive C-C and C-H bond activation reactions in the interconversion of allyl cyanide by [Ni(dippe)].三苯基硼对[Ni(dippe)]催化烯丙基腈互变中C-C和C-H键竞争活化反应的动力学、热力学及影响
J Am Chem Soc. 2004 Mar 24;126(11):3627-41. doi: 10.1021/ja037002e.
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Chem Commun (Camb). 2003 Dec 7(23):2924-5. doi: 10.1039/b311103b.
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