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

Dejian Huang; John C. Bollinger; W. E. Streib; Kirsten Folting; Victor G Young; Odile Eisenstein; Kenneth G. Caulton

doi:10.1021/om9910017

14-electron ruthenium(II) hydride, [RuH(CO)(P^tBu₂Me)₂]BAr′₄ (Ar′ = 3,5-(C₆H₃)(CF₃)₂): synthesis, structure, and reactivity toward alkenes and oxygen ligands

Dejian Huang, John C. Bollinger, W. E. Streib, Kirsten Folting, Victor G Young, Odile Eisenstein, Kenneth G. Caulton

Chemistry (Twin Cities)

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Abstract

Triflate in RuH(OTf)(CO)L₂ (L = P^tBu₂Me) 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.

Original language	English (US)
Pages (from-to)	2281-2290
Number of pages	10
Journal	Organometallics
Volume	19
Issue number	12
DOIs	https://doi.org/10.1021/om9910017
State	Published - Jun 12 2000

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title = "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",

abstract = "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.",

author = "Dejian Huang and Bollinger, {John C.} and Streib, {W. E.} and Kirsten Folting and Young, {Victor G} and Odile Eisenstein and Caulton, {Kenneth G.}",

year = "2000",

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language = "English (US)",

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T1 - 14-electron ruthenium(II) hydride, [RuH(CO)(PtBu2Me)2]BAr′4 (Ar′ = 3,5-(C6H3)(CF3)2)

T2 - synthesis, structure, and reactivity toward alkenes and oxygen ligands

AU - Huang, Dejian

AU - Bollinger, John C.

AU - Streib, W. E.

AU - Folting, Kirsten

AU - Young, Victor G

AU - Eisenstein, Odile

AU - Caulton, Kenneth G.

PY - 2000/6/12

Y1 - 2000/6/12

N2 - 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.

AB - 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.

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14-electron ruthenium(II) hydride, [RuH(CO)(P^tBu₂Me)₂]BAr′₄ (Ar′ = 3,5-(C₆H₃)(CF₃)₂): synthesis, structure, and reactivity toward alkenes and oxygen ligands

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