[Ru(η5-pentamethylcyclopentadienyl)(H)2(P(i-Pr)3)(SiPh2)]B(C6F5)4 | 1335244-46-6

• 英文名称: [Ru(η5-pentamethylcyclopentadienyl)(H)2(P(i-Pr)3)(SiPh2)]B(C6F5)4
• 英文别名: [(η5-C5Me5)(P(i-Pr)3)Ru(=SiPh2)][B(C6F5)4]
• CAS: 1335244-46-6
• 化学式: C₂₄BF₂₀*C₃₁H₄₈PRuSi
• 分子量: 1259.89
• InChiKey: KCRWRWHJMRRBSM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  二苯甲酮 、 [Ru(η5-pentamethylcyclopentadienyl)(H)2(P(i-Pr)3)(SiPh2)]B(C6F5)4 以 氟苯 为溶剂， 以87%的产率得到[(η5-C5Me5)(P(i-Pr)3)Ru(SiPh2(OCPh2))][B(C6F5)4]
  参考文献：
  名称：

  Stoichiometric Reaction Chemistry of Cationic Ruthenium Silylene Complexes toward Polar and Nonpolar Organic Substrates

  摘要：

  Reactions of the cationic ruthenium silylene complexes [Cp*((PPr3)-Pr-i)Ru(H)(2)(==SiRR')][B(C6F5)(4)] (R =Mes, R' = H, 1; R = R' = Ph, (2)) with alkenes, allcynes, ketones, and Lewis bases were explored. Addition of 1-hexene, 3,3-imethylbut-1-ene, styrene, and cyclopentene to 1 afforded the disubstituted silylene products [Cp*((PPr3)-Pr-i)Ru(H)(2)(= SiMesR)J[B(C6F5)(4)] (R = Hex, (3); R = CH(2)CH(2)(3)(t)u, (4); R CH,CH,Ph, (5); R = C5H9, (6)). Analogous reactions with 2-butyne and 3,3-dimethylbut-1-yne yielded the vinyl-substituted silylene complexes [Cp*((PPr3)-Pr-i)Ru(H)(2)(=Si(CR=CHR')Mes)][B(C6F)(4)] (R = R' = Me, 7; R = H, R' = Bu-t, 8). Complex 1 undergoes reactions with ketones to give the heteroatomsubstituted silylene complexes [Cp*((PPr3)-Pr-i)Ru(H)(2)(=Si(OCHPhR)Mes)][B(C6F)(4)] (R = Ph, 9; R = Me, 10). Interestingly, complexes 3-8 display a weak interaction between the hydride ligands and the silicon center, while 9 and 10 exhibit a relatively large interaction (as determined by (2)J(siH) values). The reaction of isocyanates with 1 resulted in the silyl complexes [Cp*((PPr3)-Pr-i)Ru(H)(2)(Si(Mes)[kappa(2)-O(CH)(NC6H4R)][B(C(6)Fs)(4)] (R = H, 11; R = CF3, 12), and an intermediate in this transformation is observed. Complex (2) was subjected to various Lewis bases to yield the base-stabilized silylene complexes [Cp*(P'Pr-3)Ru(H)(2)(SiPh2.L)][B(C6F)(4)] (L = DMAP, 13; L = Ph2CO, 14; L = PhCONH2, 15; L = NHMePh, 16, L = (BuSONH2)-Bu-t, 18), and the reaction of 1 with NHMePh gave [Cp*((PPr3)-Pr-i)Ru(H)(2)(SiHMes.NHMePh)][B(C6F)(4)].

  DOI：

  10.1021/om300390n
• 作为产物：
  描述：

  [Et3Si*toluene][B(C6F5)4] 、 [Ru(η5-pentamethylcyclopentadienyl)(P(i-Pr)3)(SiPh2(OTf))(H)2] 以 氟苯 为溶剂， 以57%的产率得到[Ru(η5-pentamethylcyclopentadienyl)(H)2(P(i-Pr)3)(SiPh2)]B(C6F5)4
  参考文献：
  名称：

  Cp*(PiPr₃)RuOTf: A Reagent for Access to Ruthenium Silylene Complexes

  摘要：

  The ruthenium triflate complex Cp*(PiPr(3))RuOTf (1) was generated from the reaction of Cp*(PiPr(3))RuCl with Me3SiOTf in dibutyl ether. Complex 1 reacted with primary and secondary silanes to produce a family of Ru(IV) silyl dihydride complexes of the type Cp*(PiPr(3))Ru(H)(2)(SiRR'OTf) (3-12). Structural analyses of complexes 8 (R = R' = Ph) and 12 (R = R' = fluorenyl) revealed the presence of a tetrahedral silicon center and a four-legged piano stool geometry about ruthenium. Anion abstraction from Cp*(PiPr(3))Ru(H)(2)(SiHROTf) by [Et3Si center dot toluene][B(C6F5)(4)] afforded hydrogen-substituted cationic ruthenium silylene complexes [Cp*(PiPr(3))Ru(H)(2)(=SiHR)][B(C6F5)(4)] (R = Mes (13), R = Si(SiMe3) (14)) that display a significant Ru-H center dot center dot center dot Si interaction, as indicated by relatively large (2)J(SiH) coupling constants ((2)J(SiH) = 58.2 Hz (13), (2)J(SiH) = 37.1 Hz (14)). The syntheses of secondary silylene complexes [Cp*(PiPr(3))Ru(H)(2)(=SiRR')][B(C6F5)(4)] (R = R' = Ph (15); R = Ph, R' = Me (16), R = R' = fluorenyl (17)) were also achieved by anion abstraction with [Et3Si center dot toluene] [B(C6F5)(4)]. Complexes 15-17 do not display strong Ru-H center dot center dot center dot Si secondary interactions, as indicated by very small (2)J(SiH) coupling constant values.

  DOI：

  10.1021/om200795x