Chasing the agostic interaction in ligand assisted cyclometallation reactions of palladium(II)

Sajjad M. Arif; Christensen Kirsten E.; Rees Nicholas H.; Schwerdtfeger Peter; Harrison John A.; Nielson Alastair J.

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Chasing the agostic interaction in ligand assisted cyclometallation reactions of palladium(II)

机译：追逐钯（II）的配体辅助环芯基反应中的骨膜相互作用

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A 500 MHz NMR study of the reaction between 1-tetralone oxime and PdCl42- in CD3OD shows resonances attributable to a potential agostic intermediate prior to the formation of the insoluble cyclopalladated product which itself was characterised by X-ray crystallography. Calculated structural, spectroscopic, QTAIM, NBO and NCI analysis results obtained from density functional theory (DFT) calculations give a full description of the putative agostic intermediate [PdCl2(1-tetralone oxime)] (1) which is shown to include a previously unrecognised pi-electron density donation from the aromatic ring to the metal in close proximity to the agostic carbon atom. Changing the (N)-OH donor to (N)-OMe does not effect the magnitude of these interactions. (N)-OH and (N)-OMe acetophenone imines in which the aromatic ring has the potential to rotate show similar agostic and pi-electron donation to the alicyclic ring counterparts. 1-Tetralone which coordinates to the metal by a Pd-O bond that is much weaker than the Pd-N complexes has a slightly stronger agostic component and slightly weaker p-electron donation than the oxime counterpart.

机译：500MHz NMR研究在CD3OD之间的1-4tetralone肟和PdCl42-中的反应研究表明，在形成不溶性环膦产物之前，其具有潜在的可扰动中间体的共振，其本身以X射线晶体学特征在一起。从密度泛函理论获得计算结构的，光谱学，QTAIM，NBO和NCI分析结果（DFT）计算得到的完整说明推定agostic中间体[加入PdCl 2（1-四氢萘酮肟）]（1），其被示出为包括以前未识别PI-电子密度从芳环捐赠给沉肠碳原子附近的金属。改变（n）-OH供体至（n）-ome不会影响这些相互作用的大小。（n）-OH和（n） - 苯乙酮酰亚胺，其中芳环具有旋转的潜力，显示出与脂环族环对应物相似的性能和PI-Electron捐赠。通过PD-O键与金属坐标的1-Tetralone通过比PD-N复合物弱得较大的粘性组分稍微较强，并且比肟对应物略微较弱的P-Electron捐赠。

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《Dalton transactions: An international journal of inorganic chemistry》 |2017年第46期|共13页
作者
Sajjad M. Arif; Christensen Kirsten E.; Rees Nicholas H.; Schwerdtfeger Peter; Harrison John A.; Nielson Alastair J.;
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Massey Univ Auckland Inst Nat &

Math Sci Chem North Shore Mail Ctr Private Bag 102904 Auckland New Zealand;

Univ Oxford Dept Chem Inorgan Chem Lab South Parks Rd Oxford QX1 3QR England;

Univ Oxford Dept Chem Inorgan Chem Lab South Parks Rd Oxford QX1 3QR England;

Massey Univ Auckland New Zealand Inst Adv Study Ctr Theoret &

Phys North Shore Mail Ctr Private Bag 102904 Auckland New Zealand;

Massey Univ Auckland Inst Nat &

Math Sci Chem North Shore Mail Ctr Private Bag 102904 Auckland New Zealand;

Massey Univ Auckland Inst Nat &

Math Sci Chem North Shore Mail Ctr Private Bag 102904 Auckland New Zealand;

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正文语种 eng
中图分类化学;无机化学;
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1. Chasing the agostic interaction in ligand assisted cyclometallation reactions of palladium(II) [J] . Sajjad M. Arif, Christensen Kirsten E., Rees Nicholas H., Dalton transactions: An international journal of inorganic chemistry . 2017,第46期

机译：追逐钯（II）的配体辅助环芯基反应中的骨膜相互作用
2. Cyclometallated gold(III) complexes with a trithiacrown ligand: Solventless Au(III) cyclometallation, intramolecular gold-sulfur interactions, and fluxional behavior in 1,4,7-trithiacyclononane Au(III) complexes [J] . Daron E. Janzen, Shannon R. Doherty, Donald G. VanDerveer, Journal of Organometallic Chemistry . 2014,第Null期

机译：具有三硫杂cro配体的环金属化金（III）配合物：1,4,7-三硫代环壬烷金（III）配合物中的无溶剂金（III）环金属化，分子内金-硫相互作用和熔体行为
3. Rhodium(III) and Iridium(III) Complexes of a NHC-Based Macrocycle: Persistent Weak Agostic Interactions and Reactions with Dihydrogen [J] . Gyton Matthew R., Leforestier Baptiste, Chaplin Adrian B. Organometallics . 2018,第21期

机译：基于NHC的宏观的铑（III）和铱（III）复合物：持续的弱恶性相互作用和二氢的反应
4. Role of the Silver Salt in the Stereoselective Ligand Exchange Reaction of the Diiodoiridium(III)Complex Bearing the Cp'-P Ligand with Triphenylphosphine in the Presence of AgOTf [C] . Takahiro Goi, Yasutaka Kataoka, Kazushi Mashima, Symposium on Organometallic Chemistry . 2003

机译：银盐在二碘辛（III）复合物的立体选择性配体交换反应中的作用，其含有三苯基膦的Cp'-P配体在agotf存在下
5. I. Multicatalysis: Development of a Bismuth(III) triflate-catalyzed Nucleophilic addition/ Hydrofunctionalization Reaction in the Synthesis of Complex Heterocycles II. C--H Arylation of Arenes and Heteroarenes with Palladium-Carboxylate Catalysts: Identification of the Catalyst Resting State and the Crucial Role of Pivalate Ligand in Stabilization of the Catalyst III. C--H Arylation of Heteroarenes with Palladium-Carboxylate Catalysts: Importance of Phosphine Ligand for Basic Heteroarene Substrates IV. C--H Arylation of Heteroarenes with Palladium-Carboxylate Catalysts: Effect of the Properties of Basic Heteroarene Substrates on Direct Arylations. [D] . Tundel, Rachel E. 2011

机译：I.多催化作用：在复杂的杂环化合物的合成中三氟甲磺酸铋（III）催化的亲核加成/加氢官能化反应的发展。羰基钯催化剂对芳烃和杂芳烃的CH-H芳基化反应：催化剂静止状态的鉴定以及新戊酸酯配体在稳定催化剂中的关键作用III。羰基钯催化剂催化杂芳烃的CH芳基化：膦配体对基础杂芳烃基质的重要性IV。杂芳烃与钯-羧酸酯的CH芳基化：碱性杂芳烃底物性能对直接芳基化的影响。
6. Rhodium(III) and Iridium(III) Complexes of a NHC-BasedMacrocycle: Persistent Weak Agostic Interactions and Reactions withDihydrogen [O] . MatthewR. Gyton, Baptiste Leforestier, Adrian B. Chaplin, -1

机译：基于NHC的铑（III）和铱（III）配合物大周期：持久弱的亲和力相互作用和与二氢
7. Chasing the agostic interaction in ligand assisted cyclometallation reactions of palladium(ii) [O] . M. Arif Sajjad, Kirsten E. Christensen, Nicholas H. Rees, 2017

机译：追逐钯（II）的配体辅助环芯基反应中的骨膜相互作用

Chasing the agostic interaction in ligand assisted cyclometallation reactions of palladium(II)

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