A cationic terminal methylene complex of Ir(I) supported by a pincer ligand

Campos J.; Peloso R.; Brookhart M.; Carmona E.

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A cationic terminal methylene complex of Ir(I) supported by a pincer ligand

机译：夹钳配体负载的Ir（I）阳离子末端亚甲基络合物

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A rare example of a cationic methylene complex of Ir(I), [(PONOP)Ir(CH_2)]~+, 2 (PONOP = 2,6-bis(di-tert-butylphosphinito) pyridine), has been prepared by α-hydride abstraction from the previously described neutral methyl complex [(PONOP)Ir(CH_3)]. The intrinsic high reactivity of the compound prevented both the isolation of a pure solid and its full characterization in the solid state. Nevertheless, the proposed molecular structure finds unequivocal support in multinuclear NMR spectroscopy and in reactivity studies that include reactions with Lewis bases, dihydrogen, and ethyl diazoacetate. An ylide compound, 3, resulted from the reaction between [(PONOP)Ir(CH_2)]~+ and PMe_3, while the η~2-alkene complex 5 formed in a C=C coupling reaction involving the methylene ligand of 2 and ethyl diazoacetate. Hydrogenolysis of the Ir=CH_2 linkage of 2 led to several, previously known, hydride and dihydrogen iridium complexes.

机译：Ir（I）的阳离子亚甲基络合物的稀有实例[[（PONOP）Ir（CH_2）]〜+，2（PONOP = 2,6-双（二叔丁基膦基吡啶）吡啶） -从先前描述的中性甲基络合物[（PONOP）Ir（CH_3）]提取-氢化物。该化合物固有的高反应活性既阻止了纯固体的分离，也阻止了其在固态下的全面表征。然而，所提出的分子结构在多核NMR光谱学和反应性研究（包括与Lewis碱，二氢和重氮乙酸乙酯的反应）中得到了明确的支持。 [[PONOP] Ir（CH_2）]〜+与PMe_3之间的反应产生了内酯化合物3，而η〜2-烯烃络合物5在C = C偶联反应中形成，涉及2的亚甲基配体和乙基重氮乙酸盐。 2的Ir = CH_2键的氢解反应产生了几种先前已知的氢化物和二氢铱配合物。

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《Organometallics》 |2013年第11期|共4页
作者
Campos J.; Peloso R.; Brookhart M.; Carmona E.;
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正文语种 eng
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cationic; methylene; complex;

机译：阳离子;亚甲基;络合物;

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专利

1. A cationic terminal methylene complex of Ir(I) supported by a pincer ligand [J] . Campos J., Peloso R., Brookhart M., Organometallics . 2013,第11期

机译：夹钳配体负载的Ir（I）阳离子末端亚甲基络合物
2. Reactivity of RhCp* Complexes Containing Labile Ligands toward Potential Linking Ligands Containing Terminal Thiophene or Furan Rings: Preparation and Structures of [Cp*Rh(L~1)Cl2], [Cp*Rh(η~2-NO3)(L~1)](OTf), and {[Rh(L~2)]·(OTf)}_∞ [L~1 = 1,2-Bis((thiophen-2-yl)methylene)hydrazine); L~2 =1,2-Bis((furan-2-yl)methylene)hydrazine] [J] . Kyung-Eun Lee, Soon W. Lee Bulletin of the Korean Chemical Society . 2010,第12期

机译：含不稳定配体的RhCp *配合物对含末端噻吩或呋喃环的潜在连接配体的反应性：[Cp * Rh（L〜1）Cl2]，[Cp * Rh（η〜2-NO3）（L〜1）的制备和结构）]（OTf），和{[Rh（L〜2）]·（OTf）} _∞[L〜1 = 1,2-双（（噻吩-2-基）亚甲基）肼）; L〜2 = 1,2-双（（呋喃-2-基）亚甲基）肼]
3. A Pd complex of a NNN pincer ligand supported on gamma-Fe2O3@SiO2 as the first magnetically recoverable heterogeneous catalyst for C-P bond forming reactions [J] . Sobhani Sara, Vahidi Zahra, Zeraatkar Zohre, RSC Advances . 2015,第46期

机译：NNN钳形配体的Pd络合物负载在γ-Fe2O3@ SiO2上，是第一个进行C-P键形成反应的磁性可回收非均相催化剂
4. Cationic Uranium Alkyl Complexes of a Rigid NON-Donor Pincer Ligand: The Impact of Arene-Coordination on Ethylene Polymerization Activity [C] . David J. H. Emslie, N. R. Andreychuk, B. Vidjayacoumar Rare Earth Research Conference . 2019

机译：刚性非供体钳配体的阳离子铀烷基复合物：芳烃配位对乙烯聚合活性的影响
5. Synthesis, characterization, and reactivity of titanium-ligand multiply bonded complexes supported by sterically encumbering β-diketiminate and PNP pincer -type ligands [D] . Bailey, Brad Cameron 2007

机译：位阻性β-二酮和PNP钳型配体支持的钛-配体多重键合配合物的合成，表征和反应性
6. Ligand survey results in identification of PNP pincer complexes of iridium as long-lived and chemoselective catalysts for dehydrogenative borylation of terminal alkynes [O] . Chun-I Lee, Jessica C. DeMott, Christopher J. Pell, 2015

机译：配体的调查结果可确定铱的PNP钳形配合物作为末端炔烃脱氢硼化的长寿命和化学选择性催化剂
7. A cationic terminal methylene complex of Ir(I) supported by a pincer ligand [O] . Campos Jesús, Peloso Riccardo, Brookhart M., 2014

机译：夹钳配体负载的Ir（I）阳离子末端亚甲基络合物

A cationic terminal methylene complex of Ir(I) supported by a pincer ligand

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