Intermetallic Cooperation in C-H Activation Involving Transient Titanium-Alkylidene Species: A Synthetic and Mechanistic Study

Carbo Jorge J.; Garcia-Lopez Diego; Gomez-Pantoja Maria; Gonzalez-Perez Juan I.; Martin Avelino; Mena Miguel; Santamaria Cristina

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Intermetallic Cooperation in C-H Activation Involving Transient Titanium-Alkylidene Species: A Synthetic and Mechanistic Study

机译：C-H激活中的金属间合作涉及促钛 - 烷基物种的C-H激活：一种合成和机械研究

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Remote carbon-hydrogen activation on titanium dinuclear complexes [{Ti(eta(5)-C5Me5)R-2}(2)(mu-O)] [R = CH2SiMe3 2, CH2CMe3 3, and CH2Ph 5) have been examined both synthetically and theoretically. While the thermal treatment of the oxoderivative [{Ti(eta(5)-C5Me5)(CH2SiMe3)(2)}(2)(mu-O)] (2) led to a series of metallacycle complexes (2a-c) by sequential carbon-hydrogen activation processes, [{Ti(eta(5)-C5Me5)(CH2CMe3)(2)}(2)(mu-O)] (3) gave rise to the formation of the metallacycle tuck-over species [Ti-2(eta(5)-C5Me5)(mu-eta(5)-C5Me4CH2-kappa C)(CH2CMe3)(mu-CH2CMe2CH2)(mu-O)] (4), as result of hydrogen abstraction from a eta(5)-C5Me5 ligand. However, the thermolysis of the tetrabenzyl complex [{Ti(eta(5)-C5Me5)(CH2Ph)(2)}(2)(mu-O)] (5) yielded the derivative [Ti-2(eta(5)-C5Me5)(mu-eta(5)-C5Me4CH2-kappa C)(CH2Ph)(3)(mu-O)] (6) that only exhibits tuck-over eta(5)-C5Me5 metalation. DFT calculations show that the mechanism involves a first alpha-hydrogen abstraction to generate a transient titanium alkylidene, which enables it to activate beta- and gamma-C(sp(3))-H bonds on the adjacent titanium center. The calculations also establish a reactivity order for the different type of gamma-H abstractions, trimethylsilyl > neopentyl congruent to benzyl, allowing us to explain the observed selectivity.

机译：远程碳 - 氢活化钛双核配合物[{钛（ETA（5）-C5Me5）R-2}（2）（MU-O）] [R = CH2SiMe3 2，新戊基3和CH2Ph 5）已经被检查两个综合和理论。虽然oxoderivative的热处理[{钛（ETA（5）-C5Me5）（CH2SiMe3）（2）} ...（2）（MU-O）]（2）导致通过一系列金属环复合物（图2a-c）中的连续的碳 - 氢活化方法，[{钛（ETA（5）-C5Me5）（新戊基）（2）} ...（2）（MU-O）]（3）引起了金属环的形成折入过物种[的Ti-2（ETA（5）-C5Me5）（MU-ETA（5）-C5Me4CH2-卡帕C）（新戊基）（MU-CH2CMe2CH2）（MU-O）]（4），如从一个ETA夺氢的结果（5）-C5Me5配体。然而，四苄复杂的热解[{钛（ETA（5）-C5Me5）（CH2Ph）（2）} ...（2）（MU-O）]（5），得到衍生物钛[Ti-2（ETA（5） -C5Me5）（MU-ETA（5）-C5Me4CH2-卡帕C）（CH2Ph）（3）（MU-O）]（6）仅表现出掖悬停ETA（5）金属化-C5Me5。 DFT计算表明，机制涉及第一α夺氢以产生一瞬态钛烷叉，其能够激活β-和γ--C（SP（3）） - 在相邻的钛中心H键。计算还建立一个反应性为了使不同类型的伽马-H抽象，三甲基甲硅烷>新戊全等于苄基，使我们能够解释所观察到的选择性。

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《Organometallics》 |2017年第16期|共8页
作者
Carbo Jorge J.; Garcia-Lopez Diego; Gomez-Pantoja Maria; Gonzalez-Perez Juan I.; Martin Avelino; Mena Miguel; Santamaria Cristina;
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作者单位

Univ Rovira &

Virgili Dept Quim Fis &

Inorgan Campus Sescelades C Marcelli Domingo S-N E-43007 Tarragona Spain;

Univ Rovira &

Virgili Dept Quim Fis &

Inorgan Campus Sescelades C Marcelli Domingo S-N E-43007 Tarragona Spain;

Univ Alcala De Henares Dept Quim Organ &

Quim Inorgan Campus Univ Madrid 28805 Spain;

Univ Alcala De Henares Dept Quim Organ &

Quim Inorgan Campus Univ Madrid 28805 Spain;

Univ Alcala De Henares Dept Quim Organ &

Quim Inorgan Campus Univ Madrid 28805 Spain;

Univ Alcala De Henares Dept Quim Organ &

Quim Inorgan Campus Univ Madrid 28805 Spain;

Univ Alcala De Henares Dept Quim Organ &

Quim Inorgan Campus Univ Madrid 28805 Spain;

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1. Intermetallic Cooperation in C-H Activation Involving Transient Titanium-Alkylidene Species: A Synthetic and Mechanistic Study [J] . Carbo Jorge J., Garcia-Lopez Diego, Gomez-Pantoja Maria, Organometallics . 2017,第16期

机译：C-H激活中的金属间合作涉及促钛 - 烷基物种的C-H激活：一种合成和机械研究
2. Dehydrofluorination of Hydrofluorocarbons by Titanium Alkylidynes via Sequential C-H/C-F Bond Activation Reactions. A Synthetic, Structural, and Mechanistic Study of 1,2-CH Bond Addition and beta-Fluoride Elimination [J] . Fout AR, Scott J, Miller DL, Organometallics . 2009,第1期

机译：钛炔烃通过连续的C-H / C-F键活化反应对氢氟烃进行脱氟化氢。 1,2-CH键加成和消除β-氟化物的合成，结构和机理研究
3. Evidence for the Existence of Terminal Scandium Imidos: Mechanistic Studies Involving Imido-Scandium Bond Formation and C-H Activation Reactions [J] . Benjamin F. Wicker, Hongjun Fan, Anne K Hickey, Journal of the American Chemical Society . 2012,第49期

机译：末端Scan亚胺存在的证据：涉及亚胺-Scan键形成和C-H活化反应的机理研究
4. Competitive Trapping of Equilibrating Pt(IV) Hydridoalkyl and Pt(II) Alkane Complexes: A Valuable Tool for the Mechanistic Investigation of C-H Activation Reactions [C] . Mats Tilset, Lars Johansson, Martin Lersch, American Chemical Society National Meeting . 2004

机译：平衡Pt（IV）氢化酰基和Pt（II）烷烃复合物的竞争诱导：一种有价值的C-H激活反应的机械研究
5. Synthetic and mechanistic studies of ruthenium catalyzed C-H and C-O bond activation reactions. [D] . Kim, Junghwa. 2016

机译：钌催化的C-H和C-O键活化反应的合成和机理研究。
6. Cationic Pd(II)-catalyzed C–H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies [O] . Takashi Nishikata, Alexander R Abela, Shenlin Huang, 2016

机译：室温下阳离子Pd（II）催化的C–H活化/交叉偶联反应：合成和机理研究
7. Oxidative C-H Activation/C-C Bond Forming Reactions: Synthetic Scope and Mechanistic Insights [O] . -1

机译：氧化C-H活化/ C-C键形成反应：合成范围和机械洞察

Intermetallic Cooperation in C-H Activation Involving Transient Titanium-Alkylidene Species: A Synthetic and Mechanistic Study

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