Internal Alkyne Isomerization to Vinylidene versus Stable π-Alkyne: Theoretical and Experimental Study on the Divergence of Analogous Cp*Ru and TpRu Systems
Internal Alkyne Isomerization to Vinylidene versus Stable π-Alkyne: Theoretical and Experimental Study on the Divergence of Analogous Cp*Ru and TpRu Systems
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DOI：
10.1021/om200273v
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发表时间：
2011-07
期刊：
影响因子：
2.8
通讯作者：
Vinay K. Singh;E. Bustelo;Isaac de los Ríos;Ignacio Macías‐Arce;M. Puerta;P. Valerga;Manuel Ángel Ortuño;Gregori Ujaque;A. Lledós
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作者：
Vinay K. Singh;E. Bustelo;Isaac de los Ríos;Ignacio Macías‐Arce;M. Puerta;P. Valerga;Manuel Ángel Ortuño;Gregori Ujaque;A. Lledós
Cp*Ru和TpRu配合物对内炔的活化分别得到π-炔和二取代亚乙烯基作为稳定的物种，即使两个系统具有相同的吡啶基膦配体（κ 2 P，N-iPr 2 PXPy，X = NH，CH 2，S）。[TpRuCl（iPr 2 PXPy）]络合物对炔酮PhC <$CCOR（R = Me，Ph）的活化使我们能够分离和表征亚稳态η1-O <$C（R）C <$CPh加合物。这些络合物在溶液和固体状态下自发异构化为亚乙烯基。动力学研究已进行了在溶液中通过31 P {1 H} NMR和在固体状态下通过IR光谱，提供Eyring和Avrami-Erofeev参数，分别。没有酮基的内部炔的活化也提供了亚乙烯基物种，但没有可分离的中间体。与TpRu体系相比，[Cp*RuCl（iPr 2 PXPy）]对炔酮的活化总是产生稳定的π-炔物种. Cp*Ru−π-炔化合物和TpRu-亚乙烯基化合物的代表已经通过B.
The activation of internal alkynes by Cp*Ru and TpRu complexes gives respectively π-alkyne and disubstituted vinylidene as stable species, even though both systems bear identical pyridylphosphine ligands (κ2P,N- iPr2PXPy, X = NH, CH2, S). The activation of the alkynones PhC≡CCOR (R = Me, Ph) by [TpRuCl(iPr2PXPy)] complexes allowed us to isolate and characterize metastable η1-O═C(R)C≡CPh adducts. These complexes isomerize spontaneously to vinylidene both in solution and in the solid state. Kinetic studies have been carried out in solution by 31P{1H} NMR and in the solid state by IR spectroscopy, providing the Eyring and Avrami–Erofeev parameters, respectively. The activation of internal alkynes without ketone groups provided vinylidene species as well, but without isolable intermediates. In contrast with the TpRu system, the activation of alkynones by [Cp*RuCl(iPr2PXPy)] always results in stable π-alkyne species. Representatives of both Cp*Ru−π-alkyne and TpRu–vinylidene compounds have been characterized b...