Primary and Secondary Phosphine Complexes of Iron Porphyrins and Ruthenium Phthalocyanine: Synthesis, Structure, and P−H Bond Functionalization

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• 作者：Jie-Sheng Huang ; Guang-Ao Yu ; Jin Xie ; Kwok-Ming Wong ; Nianyong Zhu ; Chi-Ming Che
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：October 20, 2008
• 年：2008
• 卷：47
• 期：20
• 页码：9166-9181
• 全文大小：511K
• 年卷期：v.47,no.20(October 20, 2008)
• ISSN：1520-510X

文摘

Reduction of [Fe^III(Por)Cl] (Por = porphyrinato dianion) with Na₂S₂O₄ followed by reaction with excess PH₂Ph, PH₂Ad, or PHPh₂ afforded [Fe^II(F₂₀-TPP)(PH₂Ph)₂] (1a), [Fe^II(F₂₀-TPP)(PH₂Ad)₂] (1b), [Fe^II(F₂₀-TPP)(PHPh₂)₂] (2a), and [Fe^II(2,6-Cl₂TPP)(PHPh₂)₂] (2b). Reaction of [Ru^II(Pc)(DMSO)₂] (Pc = phthalocyaninato dianion) with PH₂Ph or PHPh₂ gave [Ru^II(Pc)(PH₂Ph)₂] (3a) and [Ru^II(Pc)(PHPh₂)₂] (4). [Ru^II(Pc)(PH₂Ad)₂] (3b) and [Ru^II(Pc)(PH₂Bu^t)₂] (3c) were isolated by treating a mixture of [Ru^II(Pc)(DMSO)₂] and OPCl₂Ad or PCl₂Bu^t with LiAlH₄. Hydrophosphination of CH₂CHR (R = CO₂Et, CN) with [Ru^II(F₂₀-TPP)(PH₂Ph)₂] or [Ru^II(F₂₀-TPP)(PHPh₂)₂] in the presence of ^tBuOK led to the isolation of [Ru^II(F₂₀-TPP)(P(CH₂CH₂R)₂Ph)₂] (R = CO₂Et, 5a; CN, 5b) and [Ru^II(F₂₀-TPP)(P(CH₂CH₂R)Ph₂)₂] (R = CO₂Et, 6a; CN, 6b). Similar reaction of 3a with CH₂CHCN or MeI gave [Ru^II(Pc)(P(CH₂CH₂CN)₂Ph)₂] (7) or [Ru^II(Pc)(PMe₂Ph)₂] (8). The reactions of 4 with CH₂CHR (R = CO₂Et, CN, C(O)Me, P(O)(OEt)₂, S(O)₂Ph), CH₂C(Me)CO₂Me, CH(CO₂Me)CHCO₂Me, MeI, BnCl, and RBr (R = ⁿBu, CH₂CHCH₂, MeCCCH₂, HCCCH₂) in the presence of ^tBuOK afforded [Ru^II(Pc)(P(CH₂CH₂R)Ph₂)₂] (R = CO₂Et, 9a; CN, 9b; C(O)Me, 9c; P(O)(OEt)₂, 9d; S(O)₂Ph, 9e), [Ru^II(Pc)(P(CH₂CH(Me)CO₂Me)Ph₂)₂] (9f), [Ru^II(Pc)(P(CH(CO₂Me)CH₂CO₂Me)Ph₂)₂] (9g), and [Ru^II(Pc)(PRPh₂)₂] (R = Me, 10a; Buⁿ, 10b; Bn, 10c; CH₂CHCH₂, 10d; CH₂CCMe, 10e; CHCCH₂, 10f). X-ray crystal structure determinations revealed Fe−P distances of 2.2597(9) (1a) and 2.309(2) Å (2b·2CH₂Cl₂) and Ru−P distances of 2.3707(13) (3b), 2.373(2) (3c), 2.3478(11) (4), and 2.3754(10) Å (5b·2CH₂Cl₂). Both the crystal structures of 3b and 4 feature intermolecular C−H···π interactions, which link the molecules into 3D and 2D networks, respectively.