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Equilibria and mesomerism/valence tautomerism of group 4 metallocene complexes
Chemical Society Reviews ( IF 46.2 ) Pub Date : 2020-03-18 , DOI: 10.1039/c9cs00637k Uwe Rosenthal 1, 2, 3
Chemical Society Reviews ( IF 46.2 ) Pub Date : 2020-03-18 , DOI: 10.1039/c9cs00637k Uwe Rosenthal 1, 2, 3
Affiliation
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In this account, examples of the influence of equilibrium and mesomerism/valence tautomerism on reactions of selected group 4 metallocene complexes will be discussed. Complexes of bis(trimethylsilyl)acetylene Me3SiC2SiMe3 (mono-functional alkynes: C![[triple bond, length as m-dash]](https://www.rsc.org/images/entities/char_e002.gif)
C) in Cp′2M(η2-Me3SiC2SiMe3) (Cp′ = substituted η5-cyclopentadienyl), of α-di-Ph2P- (hetero-tri-functional: P, CC, P) in Cp′2M(η2-Ph2C2PPh2), and of α-mono-SiH- (hetero-bi-functional: CC, SiH) and α-di-SiH-substituted alkynes (hetero-tri-functional: SiH, CC, SiH) in Cp′2M(η2-Me3SiC2SiMe2H) and Cp′2M(η2-HMe2SiC2SiMe2H), respectively, were considered. Additionally, unusual all-C-metallacycles like metallacyclopentynes Cp′2M[η2-C(R2)–C2–C(R2)–] (formed by coordination of tri-functional trienes: C![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
C, CC, CC), five-membered metallacycloallenes Cp′2M[η2-C(R)CC(R)–C(R2)–] (formed by coordination of bi-functional enynes: CC, CC), metallacyclocumulenes Cp′2M[η2-C(R)CCC(R)–] (formed by coordination of bi-functional diynes: CC, CC), and seven-membered metallacyclocumulenes Cp′2M[η2-C(R)C(C2R)–C(R)CCC(R)–] (formed by coordination of two bi-functional diynes: CC, CC), with M = Ti, Zr, and Hf were selected as examples for considerations of equilibrium and mesomerism/valence tautomerism. On the basis of spectroscopic investigations, their molecular structures and selected calculations, it is discussed how the different interpretations of the equilibrium and mesomerism/valence tautomerism are in line with observed reactivity patterns.
中文翻译：
第4类茂金属配合物的平衡和介聚/价互变异构
因此，将讨论平衡和介聚/价互变异构对选定的第4族茂金属配合物反应的影响的实例。双（三甲基甲硅烷基）乙炔的Me络合物3的SiC 2森达3（单官能炔烃：CC）在'的Cp 2（η中号2 -Me 3的SiC 2森达3（=取代的η）CP' 5 -环戊二烯基，的） α二-PH 2 P-（杂三官能：P，C C，P）中的Cp' 2 M（η 2 -Ph 2 c ^ 2 PPH 2），以及α-单SiH的（杂双功能性：C C，SiH）的，α二- SiH的取代的炔（杂三官能：SiH基，C C，SiH）的在CP' 2中号（η 2 -Me 3的SiC 2森达2 H）和CP' 2 M（η 2 -HMe 2的SiC 2森达2 2H），分别考虑。另外，不寻常的所有-C-metallacycles像metallacyclopentynes CP' 2 M [η 2 -C（R 2）-C 2 -C（R 2） - ]（由三官能三烯的协调形成：C C，C C， CC），五元metallacycloallenes CP' 2 M [η 2 -C（R）Ç C（R）-C（R 2） - ]（由双官能的烯炔协调形成：C C，C C），metallacyclocumulenes CP' 2 M [η 2 -C（R）ç ç C（R） - ]（通过双官能二炔协调形成：C C，C C），和7元metallacyclocumulenes CP' 2 M [η 2 - C（R）C（C 2 R）–C（R）C C C（R）–]（由两个双功能二炔（C C，CC），其中M = Ti，Zr和Hf被选为示例，以考虑平衡和介聚/价互变异构现象。在光谱学研究，其分子结构和选择的计算的基础上，讨论了平衡和介聚/价互变异构的不同解释如何与观察到的反应模式一致。
更新日期：2020-04-24
C) in Cp′2M(η2-Me3SiC2SiMe3) (Cp′ = substituted η5-cyclopentadienyl), of α-di-Ph2P- (hetero-tri-functional: P, CC, P) in Cp′2M(η2-Ph2C2PPh2), and of α-mono-SiH- (hetero-bi-functional: CC, SiH) and α-di-SiH-substituted alkynes (hetero-tri-functional: SiH, CC, SiH) in Cp′2M(η2-Me3SiC2SiMe2H) and Cp′2M(η2-HMe2SiC2SiMe2H), respectively, were considered. Additionally, unusual all-C-metallacycles like metallacyclopentynes Cp′2M[η2-C(R2)–C2–C(R2)–] (formed by coordination of tri-functional trienes: CC, CC, CC), five-membered metallacycloallenes Cp′2M[η2-C(R)CC(R)–C(R2)–] (formed by coordination of bi-functional enynes: CC, CC), metallacyclocumulenes Cp′2M[η2-C(R)CCC(R)–] (formed by coordination of bi-functional diynes: CC, CC), and seven-membered metallacyclocumulenes Cp′2M[η2-C(R)C(C2R)–C(R)CCC(R)–] (formed by coordination of two bi-functional diynes: CC, CC), with M = Ti, Zr, and Hf were selected as examples for considerations of equilibrium and mesomerism/valence tautomerism. On the basis of spectroscopic investigations, their molecular structures and selected calculations, it is discussed how the different interpretations of the equilibrium and mesomerism/valence tautomerism are in line with observed reactivity patterns.
中文翻译：
第4类茂金属配合物的平衡和介聚/价互变异构
因此，将讨论平衡和介聚/价互变异构对选定的第4族茂金属配合物反应的影响的实例。双（三甲基甲硅烷基）乙炔的Me络合物3的SiC 2森达3（单官能炔烃：C
C）在'的Cp 2（η中号2 -Me 3的SiC 2森达3（=取代的η）CP' 5 -环戊二烯基，的） α二-PH 2 P-（杂三官能：P，C C，P）中的Cp' 2 M（η 2 -Ph 2 c ^ 2 PPH 2），以及α-单SiH的（杂双功能性：C C，SiH）的，α二- SiH的取代的炔（杂三官能：SiH基，C C，SiH）的在CP' 2中号（η 2 -Me 3的SiC 2森达2 H）和CP' 2 M（η 2 -HMe 2的SiC 2森达2 2H），分别考虑。另外，不寻常的所有-C-metallacycles像metallacyclopentynes CP' 2 M [η 2 -C（R 2）-C 2 -C（R 2） - ]（由三官能三烯的协调形成：C C，C C， CC），五元metallacycloallenes CP' 2 M [η 2 -C（R）Ç C（R）-C（R 2） - ]（由双官能的烯炔协调形成：C C，C C），metallacyclocumulenes CP' 2 M [η 2 -C（R）ç ç C（R） - ]（通过双官能二炔协调形成：C C，C C），和7元metallacyclocumulenes CP' 2 M [η 2 - C（R）C（C 2 R）–C（R）C C C（R）–]（由两个双功能二炔（C C，CC），其中M = Ti，Zr和Hf被选为示例，以考虑平衡和介聚/价互变异构现象。在光谱学研究，其分子结构和选择的计算的基础上，讨论了平衡和介聚/价互变异构的不同解释如何与观察到的反应模式一致。
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