N-Heterocyclic Carbene Analogues of Nucleophilic Phosphinidene Transition Metal Complexes.,Chemistry - A European Journal

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N-Heterocyclic Carbene Analogues of Nucleophilic Phosphinidene Transition Metal Complexes.
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-07-28 , DOI: 10.1002/chem.202003099
Adinarayana Doddi ₁ , Dirk Bockfeld ₂ , Thomas Bannenberg ₂ , Matthias Tamm ₂

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Chloride abstraction from the complexes [(η⁶‐p‐cymene){(IDipp)P}MCl] (2 a, M=Ru; 2 b, M=Os) and [(η⁵‐C₅Me₅){(IDipp)P}IrCl] (3 b, IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene) with sodium tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate (NaBAr^F) in the presence of trimethylphosphine (PMe₃), 1,3,4,5‐tetramethylimidazolin‐2‐ylidene (^MeIMe) or carbon monoxide (CO) afforded the complexes [(η⁶‐p‐cymene){(IDipp)P}M(PMe₃)]BAr^F] (4 a, M=Ru; 4 b, M=Os), [(η⁶‐p‐cymene){(IDipp)P}Os(^MeIMe)]BAr^F] (5) and [(η⁵‐C₅Me₅){(IDipp)P}IrL][BAr^F] (6, L=PMe₃; 7, L=^MeIMe; 8, L=CO). These cationic N‐heterocyclic carbene‐phosphinidene complexes feature very similar structural and spectroscopic properties as prototypic nucleophilic arylphosphinidene complexes such as low‐field ³¹P NMR resonances and short metal‐phosphorus double bonds. Density functional theory (DFT) calculations reveal that the metal‐phosphorus bond can be described in terms of an interaction between a triplet [(IDipp)P]⁺ cation and a triplet metal complex fragment ligand with highly covalent σ‐ and π‐contributions. Crystals of the C−H activated complex 9 were isolated from solutions containing the PMe₃ complex, and its formation can be rationalized by PMe₃ dissociation and formation of a putative 16‐electron intermediate [(η⁵‐C₅Me₅)Ir{P(IDipp)}I][BAr^F], which undergoes C−H activation at one of the Dipp isopropyl groups and addition along the iridium‐phosphorus bond to afford an unusual η³‐benzyl coordination mode.

中文翻译：

亲核磷亚膦过渡金属配合物的 N-杂环卡宾类似物。

从络合物 [(η ⁶ ‐ p ‐伞花烃){(IDipp)P}MCl] ( 2 a , M=Ru; 2 b , M=Os) 和 [(η ⁵ ‐C ₅ Me ₅ ){( IDipp)P}IrCl] ( 3 b , IDipp=1,3-双(2,6-二异丙基苯基)咪唑啉-2-亚基)与四[3,5-双(三氟甲基)苯基]硼酸钠(NaBAr ^F )三甲基膦 (PMe ₃ )、1,3,4,5-四甲基咪唑啉-2-亚基 ( ^Me IMe) 或一氧化碳 (CO) 的存在提供了配合物 [(η ⁶ ‐ p ‐伞花烃){(IDipp)P} M(PMe ₃ )]BAr ^F ] ( 4 a , M=Ru; 4 b , M=Os), [(η ⁶ ‐ p ‐伞花烃){(IDipp)P}Os( ^Me IMe)]BAr ^F ] ( 5 ) 和 [(η ⁵ ‐C ₅ Me ₅ ){(IDipp)P}IrL][BAr ^F ] ( 6 , L=PMe ₃ ; 7 , L= ^Me IMe ; 8 , L=CO)。这些阳离子N-杂环卡宾-次膦基配合物具有与原型亲核芳基次膦基配合物非常相似的结构和光谱性质，例如低场³¹ P NMR 共振和短金属-磷双键。密度泛函理论 (DFT) 计算表明，金属磷键可以用三重态 [(IDipp)P] ⁺阳离子与具有高度共价 σ 和 π 贡献的三重态金属络合物片段配体之间的相互作用来描述。从含有 PMe ₃络合物的溶液中分离出 C−H 活化络合物9的晶体，其形成可以通过 PMe ₃解离和假定的 16 电子中间体的形成来合理化[(η ⁵ ‐C ₅ Me ₅ )Ir{ P(IDipp)}I][BAr ^F ]，在 Dipp 异丙基之一处发生 C−H 活化，并沿铱磷键加成，形成一种不寻常的 η ³ -苄基配位模式。

更新日期：2020-10-06

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