Accessing Chelating Extended Linker Bis(NHC) Palladium(II) Complexes: Sterically Triggered Divergent Reaction Pathways

Wierenga Tanita S.; Vanston Catriona R.; Ariafard Alireza; Gardiner Michael G.; Ho Curtis C.

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Accessing Chelating Extended Linker Bis(NHC) Palladium(II) Complexes: Sterically Triggered Divergent Reaction Pathways

机译：进入螯合的扩展接头BIS（NHC）钯（II）配合物：空间引发的发散反应途径

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We have demonstrated the profound effect that the N-substituent steric bulk of ethylene-linked bis(N-heterocyclic carbene) (bis(NHC)) species has on the mechanism of their formation via Pd(OAc)(2)-assisted deprotometalations. The binding mode of an ethylene-linked bis(NHC) ligand is chelating when it bears N-2,4-Me2C6H3 substituents but forms a mono(NHC) with a pendant imidazolium group for N-2,6-iPr(2)C(6)H(3). An N-mesityl-substituted bis(NHC), with steric bulk intermediate between the two aforementioned substituents, generates a mixture of two chelating homoleptic normal/normal and heteroleptic normal/abnormal bis(NHC) complexes, as predicted by DFT calculations. Interestingly, the latter was seen to undergo facile reductive elimination, affording a novel tricyclic monodentate NHC ligand.

机译：我们已经证明了N-取代基石（N-杂环肉）（BIS（NHC））物种对其通过Pd（OAC）（2）的去离防计量计量的机理的深度影响。乙烯连接的双（NHC）配体的结合模式在承受N-2,4-ME2C6H3取代基时螯合，但是用侧咪唑基团形成单咪唑基团，用于N-2,6-IPR（2）C. （6）H（3）。由两种上述取代基之间的空料体中间体的N-乙基取代的双（NHC）产生两种螯合的常规/正常/正常/异常BIS（NHC）复合物的混合物，如DFT计算所预测的。有趣的是，后者被视为突显的还原消除，这是一种新型三环单态的NHC配体。

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《Organometallics》 |2019年第15期|共7页
作者
Wierenga Tanita S.; Vanston Catriona R.; Ariafard Alireza; Gardiner Michael G.; Ho Curtis C.;
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Univ Tasmania Sch Nat Sci Chem Hobart Tas 7001 Australia;

Univ Tasmania Sch Nat Sci Chem Hobart Tas 7001 Australia;

Univ Tasmania Sch Nat Sci Chem Hobart Tas 7001 Australia;

Univ Tasmania Sch Nat Sci Chem Hobart Tas 7001 Australia;

Univ Tasmania Sch Nat Sci Chem Hobart Tas 7001 Australia;

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1. Accessing Chelating Extended Linker Bis(NHC) Palladium(II) Complexes: Sterically Triggered Divergent Reaction Pathways [J] . Wierenga Tanita S., Vanston Catriona R., Ariafard Alireza, Organometallics . 2019,第15期

机译：进入螯合的扩展接头BIS（NHC）钯（II）配合物：空间引发的发散反应途径
2. Reduction of a Chelating Bis(NHC) Palladium(II) Complex to [{μ-bis(NHC)}2Pd2H]+: A Terminal Hydride in a Binuclear Palladium(I) Species Formed under Catalytically Relevant Conditions† [J] . Peter#x2005, D.#x2005, W. Boyd Prof., Angewandte Chemie . 2010,第36期

机译：螯合的双（NHC）钯（II）络合物还原为[{μ-bis（NHC）} 2Pd2H] +：在催化相关条件下形成的双核钯（I）物种中的末端氢化物†
3. Reduction of a Chelating Bis(NHC) Palladium(II) Complex to [{μ-bis(NHC)}2Pd2H]+: A Terminal Hydride in a Binuclear Palladium(I) Species Formed under Catalytically Relevant Conditions† [J] . Peter#x2005, D.#x2005, W. Boyd Prof., Angewandte Chemie International Edition . 2010,第36期

机译：螯合的双（NHC）钯（II）络合物还原为[{μ-bis（NHC）} 2Pd2H] +：在催化相关条件下形成的双核钯（I）物种中的末端氢化物†
4. Synthesis of Nickel(II) N-Heterocyclic Carbene (NHC) Complexes, Catalyzing Cross-coupling Reactions [C] . Kouki Matsubara, Keita Ueno Symposium on Organometallic Chemistry . 2006

机译：合成镍（II）正杂环基石（NHC）复合物，催化交叉偶联反应
5. iClick Reactions as a Modular Access to Palladium(II) and Platinum(II) Triazolato Complexes: Trends in Kinetics and Biological Activity =iClick-Reaktionen als modularer Zugang zu Palladium (II)- und Platin (II)-Triazolato-Komplexen: Trends in der Kinetik [D] . Peng, Kun. 2020

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6. Ligand Steric Effects of α-Diimine Nickel(II)and Palladium(II) Complexes in the Suzuki–Miyaura Cross-CouplingReaction [O] . Md Muktadir Talukder, John Michael O. Cue, Justin T. Miller, 2020

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8. Dialkylamino Phosphorus Metal Carbonyls. 2. Bis(diisopropylamino)phosphido and (Diisopropylamino)phosphinidene Metal Carbonyl Complexes from Reactions of Manganese and Cobalt Carbonyls with Bis(diisopropylamino)phosphine [R] . King, R. B., Fu, W. K., Holt, E. M. 1986

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Accessing Chelating Extended Linker Bis(NHC) Palladium(II) Complexes: Sterically Triggered Divergent Reaction Pathways

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