193205-72-0

Upstream product

• 148276-50-0 Ru(H)F(CO)(CH₃P(C(CH₃)3)2)2 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 198148-77-5 Ru(Ph)OTf(CO)(P(t)Bu₂Me)2 
• 274-07-7 benzo[1,3,2]dioxaborole 

Downstream Products

• 193205-75-3 [RuH(η2-CH2Cl2)(CO)(Pt-Bu2Me)2][B(3,5-C6H3(CF3)2)4] 
• 278168-39-1 [RuH(OH₂)(CO)(Pt-Bu₂Me)2][B(3,5-C₆H₃(CF₃)2)4] 
• 278168-30-2 [RuH(CO)(P(t)Bu₂Me)2]B(3,5-bis(trifluoromethyl)phenyl)4 
• 198148-83-3 [Ru(η(3)-(Me3Si)CH=CHC=CH(SiMe3))(CO)(P-t-Bu2Me)2][B(3,5-(CF3)2C6H3)4] 
• 193205-75-3 [RuH(CO)(CH₂Cl₂)(P(C₄H₉)2CH₃)2]⁽¹⁺⁾*[B(C₆H₃(CF₃)2)4]^(1-)=[RuH(CO)(CH₂Cl₂)(P(C₄H₉)2CH₃)2][B(C₆H₃(CF₃)2)4] 
• 5747-23-9 2-phenyl-1,3,2-benzodioxaborole 
• 198148-77-5 Ru(Ph)OTf(CO)(P(t)Bu₂Me)2 

Relevant academic research and scientific papers

14-electron ruthenium(II) hydride, [RuH(CO)(PtBu2Me)2]BAr′4 (Ar′ = 3,5-(C6H3)(CF3)2): synthesis, structure, and reactivity toward alkenes and oxygen ligands

Triflate in RuH(OTf)(CO)L2 (L = PtBu2Me) can be abstracted by NaBAr′4 (Ar′ = C6H3-(CF3)2) in C6H5F to give 14-electron RuH(CO)L2+, which has agostic donation by one tBu methyl group from each phosphine. This cation binds CH2Cl2 in an η2 fashion, and it binds OEt2 and H2O in the site trans to CO. It binds ethylene trans to hydride, and additional ethylene is catalytically dimerized to cis- and trans-but-2-ene at -30°C in C6H5F/toluene; this dimerization is slower in CH2Cl2 solvent. Propylene and H2C=CHF also bind to RuH-(CO)L2+ trans to hydride, and the latter is converted to ethylene and Ru/F products. Vinyl ethers seem to bind η1 via ether oxygen more than η2 via the CC bond, and trans to CO, and this species then isomerizes to the RuL2(CO)(η2-CH2CH2OR) insertion product at -60°C. In contrast, 2,3-dihydrofuran gives a cyclic oxygen-stabilized carbene complex. A discussion of the results based on DFT (B3PW91) calculations is presented in the following paper.

14-Electron four-coordinate Ru(II) carbyl complexes and their five-coordinate precursors: Synthesis, double agostic interactions, and reactivity

The structure of five-coordinate Ru(II) complexes RuHCl(CO)(PiPr3)2,1, RuCl2(CO)(PiPr3)2, 2, and Ru(Ph)Cl(CO)(PtBu2Me)2, 12, are reported. All three of these complexes have square-based pyramid geometry with the strongest σ-donor ligand trans to the vacant site. These 16-electron complexes do not show bona fide agostic interactions. This is attributed to the strong trans influence ligand (H, CO, and Ph) and π-donation of the Cl, which is further supported by the fact that two agostic interactions are present in the Cl- removal product of 12, i.e., the four-coordinate [RuPh(CO)L2]BAr′4 (L = PtBu2Me, Ar′ = 3,5-C6H3(CF3)2), 16. Structural comparison of 16 and 12 reveals that removal of Cl- does not change the remaining ligand arrangements but creates two low-lying LUMOs for agostic interactions, which persist in solution as evidenced by IR spectroscopy. Reactions of 16 with E-H (E = B, C(sp)) bonds cleave the Ru-Ph bond and form Ru-E/H bonds by different mechanisms. The reaction with catecholborane gives [RuH(CO)L2]BAr′4, which further reacts with catecholborane to give [Ru(BR2)(CO)L2]BAr′4. However, the reaction with Me3SiCCH undergoes a multistep transformation to give a PhCCSiMe3- and Me3SiCCH-coupled product, the mechanism of which is discussed. Reaction of RuCl2(CO)L2 with 1 equiv MeLi affords RuMeCl(CO)L2, 5, which further reacts with MeLi forming RuMe2(CO)L2, 7. Variable-temperature 13C{1H} NMR spectra reveal the two methyls in 7 are inequivalent and exchange by overcoming an energy barrier of 6.8 kcal/mol at -30 °C. The chloride of 5 can be removed to give [RuMe(CO)L2]BAr′4.