356793-67-4

Upstream product

• 168153-18-2 [Li(OEt₂)₂][B(C₆F₅)₄] 
• 60-29-7 diethyl ether 
• 356793-64-1 [((CH₃)5C₅)IrH(P(CH₃)3)(CH₂Si(CH₃)2)]⁽¹⁺⁾*B(C₆F₅)4^(1-)=[((CH₃)5C₅)IrH(P(CH₃)3)(CH₂Si(CH₃)2)](B(C₆F₅)4) 

Downstream Products

• 356793-69-6 [((CH₃)5C₅)Ir(P(CH₃)3)(CH₃)(Si(CH₃)2NC₅H₅)]⁽¹⁺⁾*B(C₆F₅)4^(1-)=[((CH₃)5C₅)Ir(P(CH₃)3)(Si(CH₃)3(NC₅H₅))](B(C₆F₅)4) 
• 356793-74-3 [((CH₃)5C₅)Ir(P(CH₃)3)(C₂H₄)(Si(CH₃)3)]⁽¹⁺⁾*B(C₆F₅)4^(1-)=[((CH₃)5C₅)Ir(P(CH₃)3)(C₂H₄)(Si(CH₃)3)](B(C₆F₅)4) 
• 356793-71-0 [((CH₃)5C₅)Ir(P(CH₃)3)(CO)(Si(CH₃)3)]⁽¹⁺⁾*B(C₆F₅)4^(1-)=[((CH₃)5C₅)Ir(P(CH₃)3)(CO)(Si(CH₃)3)](B(C₆F₅)4) 

Relevant academic research and scientific papers

Reactions of Cp*(PMe3)Ir(Me)OTf with silanes: Role of base-free silylene complexes in rearrangements of the resulting silicon-based ligands

The mechanisms of silicon-hydrogen activation by Cp*(PMe3)Ir(Me)OTf (Cp* = η5-C5-Me5, OTf = OSO2CF3; 1) and rearrangements of the resulting silyliridium complexes were investigated. The scope of this reaction has been studied for silanes with a variety of substituents. Silylene complexes of the type [Cp*(PMe3)Ir(SiR2)(H)] [X] (X = OTf, R = Mes, 6; X = B(C6F5)4, R = Ph, 16) have been isolated, and the likelihood of their involvement in the rearrangements is discussed. The kinetics of the isomerization reaction of the cyclometalated iridium(V) complex {Cp*(PMe3)Ir(H)[κ2-SiH(Mes)(2-CH2-4 ,6-Me2C6H2)]}[OTf] (5) to the iridium silylene [Cp*(PMe3)Ir(SiMes2)(H)] [OTf] (6) were examined using NMR spectroscopic techniques. The primary kinetic isotope effect (Si-H vs Si-D bond) for this process was determined to be 1.4 ± 0.1, implying a rate-limiting hydride migration from silicon to iridium. The activation parameters for this isomerization have also been measured: ΔH? = 23 ± 2 kcal/mol and ΔS? = 0.1 ± 0.01 eu. Slow hydride migration to produce a silylene complex from either Cp*(PMe3)Ir(Me)OTf (1) or [Cp*(PMe3Ir(Me)(CH2Cl2)][BC6F 5)4] (17) is observed for large substituents on silicon. However, production of the sterically less crowded complex [Cp*(PMe3)Ir(SiPh2)(H)] [B(C6F5)4] (16) is extremely rapid upon reaction of 17 with H2SiPh2. This argues for the intermediacy of a three-coordinate silicon species.

An observable silene/silylene rearrangement in a cationic iridium complex

The iridium complex Cp*(PMe3)Ir(Me)(SiMe2-OTf) (2) reacts with LiB(C6F5)4(Et2O)2 to form a mixture of the silene complex [Cp*(PMe3)Ir(η2-CH2SiMe2) (H)]- [B(C6F5)4] (3) and the base-stabilized silylene complex [Cp*(PMe3)Ir(Me)(SiMe2(Et2O))] [B(C6F5)4] (4). The silene complex 3 has been crystallographically characterized. Addition of pyridine to this mixture affords Cp*(PMe3)-Ir(Me)(SiMe2(L)][B(C6 F5)4] (5a, L = pyridine) in good yield, whereas addition of CO or ethylene results in clean formation of Cp*(PMe3)Ir(L)(SiMe3)][B(C6F5) 4] (8a, L = CO; 8b, L = C2H4).