Exceptionally facile CO addition to a saturated ruthenium complex.

Exceptionally facile CO addition to a saturated ruthenium complex. Research Abstract Details 

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Exceptionally facile CO addition to a saturated ruthenium complex. Abstract Text:

Christine Bibal,Yegor D Smurnyy,Maren Pink,Kenneth G Caulton,

Synthesis and characterization of Cp*Ru[eta3-HC(PPh2NPh)2], 1, reveals it to have a "piano stool" structure with the ligand bound to Ru(II) via two N and the unique, sp3 hybridized carbon. While the analogous (cymene) Ru[eta3-HC(PPh2NPh)2]+ does not react with CO, under the same conditions, 1 adds one CO rapidly (25 degrees C, 1 atm CO). Characterization, including an X-ray structure determination, shows that CO has displaced one chelate ligand nitrogen, which then hangs off the molecule, free of Ru. DFT calculations reveal a possible mechanism via a remarkably low energy (+9.3 kcal/mol) intermediate, pendant N, but with one phenyl on phosphorus stabilizing Ru via donation from a C(ipso)=C(ortho) bond. DFT calculations show that the electronic energy change for binding CO is over 20 kcal/mol less favorable for cymene than for C5Me5- as ligand; the reactivity difference is thus thermodynamic in origin.

Exceptionally facile CO addition to a saturated ruthenium complex. Publishing Authors By Initials

C Bibal,YD Smurnyy,M Pink,KG Caulton,

For similar inorganic chemicals: ruthenium compounds research abstracts see: inorganic chemicals: ruthenium compounds research

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Exceptionally facile CO addition to a saturated ruthenium complex. Journal Published:

PUBLICATION TYPE: Research Support, U.S. Gov't,

Journal: Journal of the American Chemical Society

VOLUME: 127

Page Numbers: 8944-5

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 29

MONTH: Jun

YEAR: 2005

Exceptionally facile CO addition to a saturated ruthenium complex. Information

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LANGUAGE: eng

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Exceptionally facile CO addition to a saturated ruthenium complex. Keywords Mesh Terms:

KEYWORDS: Ruthenium Compounds

MESH TERMS: chemistry

Chemical & Substance for Abstract: Exceptionally facile CO addition to a saturated ruthenium complex. Information

Substance Name: Ruthenium

Registry Number: 7440-18-8

Grant and Affiliation Information for Exceptionally facile CO addition to a saturated ruthenium complex.

AFFILIATION: Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, Indiana 47405, USA.

Country: United States

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MEDLINETA: J Am Chem Soc

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