O-Protonation of the (μ-H)Bιι3(μ-ΟΟ)(ΟΟ)10 Anion. Rearrangement of (m-h)ru3(m-coh)(CO)10 to H(M-H)Ru3(CO)11. Kinetics of Reductive Elimination of Hydrogen from H(-H)Ru3(CO)11

Leigh R. Nevinger; Jerome B. Keister; John Maher

doi:10.1021/om00156a033

O-Protonation of the (μ-H)Bιι₃(μ-ΟΟ)(ΟΟ)₁₀ Anion. Rearrangement of (m-h)ru₃(m-coh)(CO)₁₀ to H(M-H)Ru₃(CO)₁₁. Kinetics of Reductive Elimination of Hydrogen from H(-H)Ru₃(CO)₁₁

Leigh R. Nevinger
, Jerome B. Keister
, John Maher

Chemistry

SUNY Buffalo
University of Bristol

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

The kinetic product from protonation of [^-H)Ru₃(m-CO)(CO)₁₀]~ with CF₃S0₃H is (^-H)Ru₃(/i-COH)(CO)₁₀. This product rearranges to H(m-H)Ru₃(CO)_n within 20 s at 25 °C. Alternatively, H(μ-H)Ru₃(CO)_u is the only product formed by protonation with CF₃C0₂H. Products were characterized by *H NMR spectroscopy at low temperatures and by FT-IR spectroscopy at ambient temperature. H(μ-H)Ru₃(CO)_u is isostructural with the Os analogue, having one bridging and one terminal hydride ligand; these hydrides undergo exchange on the NMR time scale (AG* = 51.9 kJ/mol at 236 K). H^-H)Ru₃(CO)_ndecomposes rapidly (fc(298 K) = (1.27 ± 0. 19) χ 10^-2 s^-1) to Ru₃(CO)₁₂ and hydrogen. Activation parameters (AH* = 124 (6) kJ/mol, AS* = 136 (20) J/(K mol)) and the deuterium kinetic isotope effect (k_H/k_O= 1.12 (0.09) at 298 K) were determined by using stopped-flow FT-IR spectroscopy.

Original language	English
Pages (from-to)	1900-1905
Number of pages	6
Journal	Organometallics
Volume	9
Issue number	6
DOIs	https://doi.org/10.1021/om00156a033
State	Published - 1990

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@article{48218b153e734e1487deba82e918a8e1,

title = "O-Protonation of the (μ-H)Bιι3(μ-ΟΟ)(ΟΟ)10 Anion. Rearrangement of (m-h)ru3(m-coh)(CO)10 to H(M-H)Ru3(CO)11. Kinetics of Reductive Elimination of Hydrogen from H(-H)Ru3(CO)11",

abstract = "The kinetic product from protonation of [\textasciicircum{}-H)Ru3(m-CO)(CO)10]\textasciitilde{} with CF3S03H is (\textasciicircum{}-H)Ru3(/i-COH)(CO)10. This product rearranges to H(m-H)Ru3(CO)n within 20 s at 25 °C. Alternatively, H(μ-H)Ru3(CO)u is the only product formed by protonation with CF3C02H. Products were characterized by *H NMR spectroscopy at low temperatures and by FT-IR spectroscopy at ambient temperature. H(μ-H)Ru3(CO)u is isostructural with the Os analogue, having one bridging and one terminal hydride ligand; these hydrides undergo exchange on the NMR time scale (AG* = 51.9 kJ/mol at 236 K). H\textasciicircum{}-H)Ru3(CO)ndecomposes rapidly (fc(298 K) = (1.27 ± 0. 19) χ 10-2 s-1) to Ru3(CO)12 and hydrogen. Activation parameters (AH* = 124 (6) kJ/mol, AS* = 136 (20) J/(K mol)) and the deuterium kinetic isotope effect (kH/kO= 1.12 (0.09) at 298 K) were determined by using stopped-flow FT-IR spectroscopy.",

author = "Nevinger, \{Leigh R.\} and Keister, \{Jerome B.\} and John Maher",

year = "1990",

doi = "10.1021/om00156a033",

language = "English",

volume = "9",

pages = "1900--1905",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "6",

}

TY - JOUR

T1 - O-Protonation of the (μ-H)Bιι3(μ-ΟΟ)(ΟΟ)10 Anion. Rearrangement of (m-h)ru3(m-coh)(CO)10 to H(M-H)Ru3(CO)11. Kinetics of Reductive Elimination of Hydrogen from H(-H)Ru3(CO)11

AU - Nevinger, Leigh R.

AU - Keister, Jerome B.

AU - Maher, John

PY - 1990

Y1 - 1990

N2 - The kinetic product from protonation of [^-H)Ru3(m-CO)(CO)10]~ with CF3S03H is (^-H)Ru3(/i-COH)(CO)10. This product rearranges to H(m-H)Ru3(CO)n within 20 s at 25 °C. Alternatively, H(μ-H)Ru3(CO)u is the only product formed by protonation with CF3C02H. Products were characterized by *H NMR spectroscopy at low temperatures and by FT-IR spectroscopy at ambient temperature. H(μ-H)Ru3(CO)u is isostructural with the Os analogue, having one bridging and one terminal hydride ligand; these hydrides undergo exchange on the NMR time scale (AG* = 51.9 kJ/mol at 236 K). H^-H)Ru3(CO)ndecomposes rapidly (fc(298 K) = (1.27 ± 0. 19) χ 10-2 s-1) to Ru3(CO)12 and hydrogen. Activation parameters (AH* = 124 (6) kJ/mol, AS* = 136 (20) J/(K mol)) and the deuterium kinetic isotope effect (kH/kO= 1.12 (0.09) at 298 K) were determined by using stopped-flow FT-IR spectroscopy.

AB - The kinetic product from protonation of [^-H)Ru3(m-CO)(CO)10]~ with CF3S03H is (^-H)Ru3(/i-COH)(CO)10. This product rearranges to H(m-H)Ru3(CO)n within 20 s at 25 °C. Alternatively, H(μ-H)Ru3(CO)u is the only product formed by protonation with CF3C02H. Products were characterized by *H NMR spectroscopy at low temperatures and by FT-IR spectroscopy at ambient temperature. H(μ-H)Ru3(CO)u is isostructural with the Os analogue, having one bridging and one terminal hydride ligand; these hydrides undergo exchange on the NMR time scale (AG* = 51.9 kJ/mol at 236 K). H^-H)Ru3(CO)ndecomposes rapidly (fc(298 K) = (1.27 ± 0. 19) χ 10-2 s-1) to Ru3(CO)12 and hydrogen. Activation parameters (AH* = 124 (6) kJ/mol, AS* = 136 (20) J/(K mol)) and the deuterium kinetic isotope effect (kH/kO= 1.12 (0.09) at 298 K) were determined by using stopped-flow FT-IR spectroscopy.

UR - https://www.scopus.com/pages/publications/0001200606

U2 - 10.1021/om00156a033

DO - 10.1021/om00156a033

M3 - Article

AN - SCOPUS:0001200606

SN - 0276-7333

VL - 9

SP - 1900

EP - 1905

JO - Organometallics

JF - Organometallics

IS - 6

ER -

O-Protonation of the (μ-H)Bιι₃(μ-ΟΟ)(ΟΟ)₁₀ Anion. Rearrangement of (m-h)ru₃(m-coh)(CO)₁₀ to H(M-H)Ru₃(CO)₁₁. Kinetics of Reductive Elimination of Hydrogen from H(-H)Ru₃(CO)₁₁

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