The transient titanocene(II): Direct synthesis from solvated titanium(II) chloride and cyclopentadienylsodium and ensuing interception with diphenylacetylene as 1,1-bis(cyclopentadienyl)-2,3,4,5-tetraphenyltitanacyclopentadiene

Eisch JJ; Adeosun AA; Birmingham JM

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The transient titanocene(II): Direct synthesis from solvated titanium(II) chloride and cyclopentadienylsodium and ensuing interception with diphenylacetylene as 1,1-bis(cyclopentadienyl)-2,3,4,5-tetraphenyltitanacyclopentadiene

机译：瞬变二茂钛（II）：由氯化钛（II）和环戊二烯基钠直接合成，随后被二苯基乙炔作为1,1-双（环戊二烯基）-2,3,4,5-四苯基噻吩并环戊二烯截获

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For the first time the unstable titanocene(II) has been directly synthesized by the Wilkinson metallocene approach, namely the interaction of a THF-soluble form of titanium(II) chloride with two equivalents of cyclopentadienylsodium in THF solution at 0 degrees-25 degrees C. Because of the transient existence of the titanocene(II) thereby obtained, it could only be chemically trapped in high yield as 1,1-bis(cyclopentadienyl)-2,3,4,5-tetraphenyltitanacyclopentadiene by two equivalents of diphenylacetylene, if the acetylene was added at 25 degrees C, without removal of the by-product LiCl and NaCl. If the addition of the acetylene was delayed, in order to filter off the LiCl and NaCl from the reaction mixture, then no trace of the titanacyclopentadiene derivative was found upon hydrolytic workup. Instead, a significant portion of the acetylene was found to have undergone hydrotitanation. This finding is clear evidence that the titanocene(II) had undergone a precedented rearrangement to a known dimer having the structure of a titanocene(III) hydride with a fulvalene bridge between the titanium centers. We suggest that the LiCl and NaCl present in the unfiltered reaction mixture form a dichloro complex with titanocene(II) and thereby retard its dimerizing rearrangement to the titanocene(III) hydride. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007).

机译：首次通过威尔金森茂金属方法直接合成了不稳定的钛茂（II），即，THF溶解形式的氯化钛（II）与两当量的环戊二烯基钠在THF溶液中于0-25°C下相互作用由于由此获得的二茂钛（II）的瞬时存在，它只能以高收率化学捕集为1,1-双（环戊二烯基）-2,3,4,5-四苯基噻吩并环戊二烯，当量为二苯基乙炔，如果在25℃下加入乙炔，而不除去副产物LiCl和NaCl。如果延迟乙炔的添加，为了从反应混合物中滤出LiCl和NaCl，则在水解后处理中未发现痕量的钛环戊二烯衍生物。取而代之的是，发现很大一部分的乙炔已经进行了氢化钛化。该发现清楚地表明，钛茂（II）已经进行了先有的重排，成为已知的具有钛氢化物（III）氢化物的结构的二聚体，在钛中心之间具有富瓦烯桥。我们建议存在于未过滤的反应混合物中的LiCl和NaCl与二茂钛（II）形成二氯配合物，从而阻止其二聚重排为二茂钛（III）氢化物。（（c）Wiley-VCH Verlag GmbH＆Co.KGaA，69451 Weinheim，Germany，2007）。

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《European journal of inorganic chemistry》 |2007年第26期|共5页
作者
Eisch JJ; Adeosun AA; Birmingham JM;
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正文语种 eng
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titanocene(II); Wilkinson metallocene synthesis; epititanation; 1; 1-bis(cyclopentadienyl)titanacyclopropenes; 1.1-bis(cyclopentadienyl)titanacyclopentadienes; EPIMETALLATION; DERIVATIVES; COMPLEXES; CHEMISTRY; REAGENTS;

机译：钛茂（II）;Wilkinson茂金属合成;表观烷基化;1;1-双（环戊二烯基）噻吩环丙烯;1.1-双（环戊二烯基）噻吩环戊二烯;缩聚;衍生物;化合物;化学性质;试剂;

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1. The transient titanocene(II): Direct synthesis from solvated titanium(II) chloride and cyclopentadienylsodium and ensuing interception with diphenylacetylene as 1,1-bis(cyclopentadienyl)-2,3,4,5-tetraphenyltitanacyclopentadiene [J] . Eisch JJ, Adeosun AA, Birmingham JM European journal of inorganic chemistry . 2007,第26期

机译：瞬变二茂钛（II）：由氯化钛（II）和环戊二烯基钠直接合成，随后被二苯基乙炔作为1,1-双（环戊二烯基）-2,3,4,5-四苯基噻吩并环戊二烯截获
2. Synthesis of bis(cyclopentadienyl) titanium(IV) and zirconium(IV) chlorides with 1,1'-diacetylruthenocenyl bis(hydrazones), Formation of trimetallic derivatives [J] . K. Kamalaker Reddy, M. Sayaji Rao, T. Naveenkumar Der Pharmacia Lettre . 2015,第7期

机译：用1,1'-二乙酰基钌烯基双（）合成双（环戊二烯基）钛（IV）和氯化锆（IV），形成三金属衍生物
3. Synthesis of bis(cyclopentadienyl) titanium(IV) and zirconium(IV) chlorides with 1,1'-diacetylruthenocenyl bis(hydrazones), Formation of trimetallic derivatives [J] . K. Kamalaker Reddy, M. Sayaji Rao, T. Naveenkumar Der Pharmacia Lettre . 2015,第7期

机译：用1,1'-二乙酰基钌烯基双（）合成双（环戊二烯基）钛（IV）和氯化锆（IV），形成三金属衍生物
4. Exploratory studies in free radical chemistry: Chapter 1. Use of bis(cyclopentadienyl)titanium(III) chloride as a single electron reductant. Chapter 2. Titanium(III) mediated pent-4-enyl radical cyclizations. Chapter 3. Tributyltin mediated hept-6-enyl radical cyclizations: Synthesis of thionocarbonates and thiocarbamates. [D] . Bliss, Brian Irving Alban. 2000

机译：自由基化学的探索性研究：第1章。氯化双（环戊二烯基）钛（III）作为单电子还原剂的用途。第2章。钛（III）介导的戊4烯基自由基环化。第3章。三丁基锡介导的庚6-烯基自由基环化：硫代碳酸酯和硫代氨基甲酸酯的合成。
5. In Search for Titanocene Complexes with Improved Cytotoxic Activity: Synthesis X-Ray Structure and Spectroscopic Study of Bis(η5-cyclopentadienyl)difluorotitanium(IV) [O] . Elias Koleros, Theocharis C. Stamatatos, Vassilis Psycharis, 2010

机译：寻找具有改善的细胞毒活性的钛茂复合物：Bis（η）的合成X射线结构和光谱研究5-环戊二烯基）二氟钛（IV）
6. SYNTHESIS AND STRUCTURE OF BIS(PHENYLTETRAMETHYLCYCLOPENTADIENYL)TITANIUM(III) HYDRIDE - THE FIRST MONOMERIC BIS(CYCLOPENTADIENYL)TITANIUM(III) HYDRIDE:The First Monomeric Bis(cyclopentadienyl)titanium(III) Hydride [O] . de Wolf J.M., Meetsma A., Teuben J.H 1995

机译：双（邻苯二甲基环戊二烯基）钛（III）氢化物的合成与结构
7. Synthesis of Tetraphenylstannacyclopentadienes (Stannoles). II. Derivatives and Adducts of 1,1-Dihalo-2,3,4,5-tetraphenylstannoles [R] . Gustavson, W. A., Principe, L. M., Min Rhee, W. Z., 1981

机译：四苯基环烷基环戊二烯（stannoles）的合成。 II。 1,1-二卤-2,3,4,5-四苯基锡的衍生物和加合物

The transient titanocene(II): Direct synthesis from solvated titanium(II) chloride and cyclopentadienylsodium and ensuing interception with diphenylacetylene as 1,1-bis(cyclopentadienyl)-2,3,4,5-tetraphenyltitanacyclopentadiene

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