Rhodium(III) and Iridium(III) Complexes of a Neopentyl-Substituted PNP Pincer Ligand that Feature Agostic Interactions,Organometallics

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Rhodium(III) and Iridium(III) Complexes of a Neopentyl-Substituted PNP Pincer Ligand that Feature Agostic Interactions
Organometallics ( IF 2.5 ) Pub Date : 2024-05-03 , DOI: 10.1021/acs.organomet.4c00081
Jennifer E. Smart ₁ , Ivan Prokes ₁ , Baptiste Leforestier ₂ , Adrian B. Chaplin ₁

Affiliation

The synthesis and characterization of five-coordinate rhodium(III) and iridium(III) complexes of the form [M(PNP-Np)(biph)][BAr^F₄] are described, where PNP-Np is the neopentyl-substituted pincer ligand 2,6-(Np₂PCH₂)₂C₅H₃N (Np = CH₂tBu), biph = 2,2′-biphenyl, and Ar^F = 3,5-(CF₃)₂C₆H₃. These complexes are notable for the adoption of δ-agostic interactions in the solid state, as evidenced by X-ray crystallography (50–150 K) and ATR-IR spectroscopy, but are structurally dynamic in solution, exhibiting pseudorotation of the biph ligand on the ¹H NMR time scale (185–308 K). The strength of the agostic interactions is discussed with reference to the known tert-butyl-substituted analogues [M(PNP-tBu)(biph)][BAr^F₄], probed by reaction with carbon monoxide, and quantified computationally through NBO analysis, from which the conclusion is that 3-center–2-electron bonding increases in the order M = Ir > Rh (cf. 1.5× greater perturbation energy) and pincer ligand = PNP-Np > PNP-tBu (cf. 3.3× greater perturbation energy).

中文翻译：

新戊基取代的 PNP 钳形配体的铑 (III) 和铱 (III) 配合物具有无控制相互作用

[M(PNP-Np)(biph)][BAr ^F ₄ ] 形式的五配位铑(III)和铱(III)配合物的合成和表征如下描述，其中 PNP-Np 是新戊基取代的钳配体 2,6-(Np ₂ PCH ₂ ) ₂ C ₅ H ₃ N (Np = CH ₂ tBu)，biph = 2,2′-联苯，Ar ^F = 3,5-(CF ₃ ) ₂ C ₆ H ₃ 。 X 射线晶体学 (50-150 K) 和 ATR-IR 光谱证明了这些配合物在固态中采用 δ-agostic 相互作用，但在溶液中具有结构动态，表现出 biph 配体的假旋转 ¹ H NMR 时标 (185–308 K)。参考已知的叔丁基取代的类似物 [M(PNP-tBu)(biph)][BAr ^F ₄ ] 讨论了激动相互作用的强度，通过以下方法探测与一氧化碳反应，并通过 NBO 分析进行计算量化，得出的结论是 3-中心-2-电子键合按 M = Ir > Rh（参见 1.5× 更大扰动能）的顺序增加，钳形配体 = PNP- Np > PNP-tBu（参见 3.3 倍更大的扰动能量）。

更新日期：2024-05-03

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