2-Pyridone-stabilized iridium silylene/silyl complexes: structure and QTAIM analysis,Dalton Transactions

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2-Pyridone-stabilized iridium silylene/silyl complexes: structure and QTAIM analysis
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-11-19 , DOI: 10.1039/d0dt03326j
Jefferson Guzmán _{1,

2,

3,

4,

5} , Ana M. Bernal _{1,

2,

3,

4,

5} , Pilar García-Orduña _{1,

2,

3,

4,

5} , Fernando J. Lahoz _{1,

2,

3,

4,

5} , Víctor Polo _{3,

4,

5,

6,

7} , Francisco J. Fernández-Alvarez _{1,

2,

3,

4,

5}

Affiliation

Iridium(III) complexes of the general formula [Ir(X)(κ²-NSi^iPr2)₂] (NSi^iPr2 = (4-methyl-pyridine-2-yloxy)diisopropylsilyl; X = Cl, 3; CF₃SO₃, 5; CF₃CO₂, 6) have been prepared and fully characterized, including X-ray diffraction studies and theoretical calculations. The presence of isopropyl substituents at the silicon atom favours the monomeric structure found in complexes 3 and 5. The short Ir–Si bond distances (2.25–2.28 Å) indicate some degree of base-stabilized silylene character of the Ir–Si bond in 3, 5 and 6 assisted by the 2-pyridone moiety. However, the shortening of these Ir–Si bonds might be a consequence of the constrained 2-pyridone geometry, and consequently the silyl character of these bonds can not be excluded. A DFT theoretical study on the nature of the Ir–Si bonds has been performed for complex 3 as well as for four other iridium complexes finding representative examples of different bonding situations between Ir and Si atoms: silylene, base-assisted silylene (both with an anionic base and with a neutral base), and silyl bonds, using the topological properties of the electron charge density. The results of these studies show that the Ir–Si bonds in Ir–NSi^iPr2 complexes can be considered as an intermediate between the base-stabilized silylene and silyl cases, and therefore they have been proposed as 2-pyridone-stabilized iridium silylene/silyl bonds.

中文翻译：

2-吡啶酮稳定的铱甲硅烷基/甲硅烷基络合物：结构和QTAIM分析

铱（III通式）配合物的[Ir（X）（κ ² -NSi ^IPR2）₂ ]（NSI ^IPR2 =（4-甲基-吡啶-2-基氧基）二异丙; X =氯，3 ; CF ₃ SO ₃，5 ; CF ₃ CO ₂，6）已经制备和完全表征，包括X射线衍射研究和理论计算。硅原子上异丙基取代基的存在有利于配合物3和5中的单体结构。短的Ir-Si键距离（2.25-2.28埃）表示在一定程度上的Ir-Si键的碱稳定的亚甲硅基字符的3，5和6由2-吡啶酮部分协助。但是，这些Ir-Si键的缩短可能是2-吡啶酮几何结构受约束的结果，因此不能排除这些键的甲硅烷基特性。DFT理论研究了对于复杂3的Ir-Si键的性质以及其他四个铱配合物，找到了Ir和Si原子之间不同键合情况的代表实例：甲硅烷基，碱辅助的甲硅烷基（均具有阴离子碱和中性碱）和甲硅烷基键，并利用电子电荷密度。这些研究的结果表明，Ir–NSi ^iPr2配合物中的Ir–Si键可被认为是碱稳定的甲硅烷基和甲硅烷基之间的中间物，因此，它们被建议用作2-吡啶酮稳定的铱甲硅烷基/甲硅烷基。债券。

更新日期：2020-11-25

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