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Ligand substitution from the (eta(5)-DMP)Mn(CO)(2)(Solv) [DMP=2,5-dimethylpyrrole, Solv = solvent] complexes: To ring slip or not to ring slip?

Author(s): Swennenhuis, BHG (Swennenhuis, Bert H. G.); Poland, R (Poland, Ross); Fan, WY (Fan, Wai Yip); Darensbourg, DJ (Darensbourg, Donald J.); Bengali, AA (Bengali, Ashfaq A.) Source: INORGANIC CHEMISTRY, 49 (16): 7597-7604 AUG 16 2010

The mechanism and energetics of the displacement of solvent from photolytically generated (eta(5)-DMP)Mn(CO)(2)(Solv) complexes has been studied [DMP = 2,5-dimethylpyrrole, Solv = solvent]. Rate enhancement relative to the eta(5)-cyclopentadienyl (Cp) system is not observed in the displacement of weakly bound solvents. The bond dissociation enthalpies obtained from the kinetic analysis are in good agreement with the values obtained by detailed density functional theory (DFT) calculations. The results indicate that for both the Cp and the DMP based systems the displacement of weakly bound solvents proceeds by a dissociative or I-d mechanism. This is in sharp contrast to CO displacement from (eta(5)-DMP)Mn(CO)(3), which is known to proceed by an associative mechanism by way of an eta(3) ring slip intermediate. The associative substitution pathway only becomes competitive with the dissociative channel when the Mn-Solv bond dissociation enthalpy is more than 33 kcal/mol.

Author(s):  Swennenhuis, BHG (Swennenhuis, Bert H. G.); Poland, R (Poland, Ross); Fan, WY (Fan, Wai Yip); Darensbourg, DJ (Darensbourg, Donald J.); Bengali, AA (Bengali, Ashfaq A.)
Source:  INORGANIC CHEMISTRY, 49 (16): 7597-7604 AUG 16 2010
Language:  English
Document Type:  Article
KeyWords Plus:  C-H ACTIVATION; INDENYL COMPLEXES; MANGANESE TRICARBONYLS; HOMOGENEOUS CATALYSIS; METAL-CARBONYLS; BOND STRENGTH; SPECTROSCOPY; REACTIVITY; MECHANISM; CYCLOPENTADIENYL
Addresses:  Poland, Ross; Darensbourg, Donald J.] Texas A&M Univ, Dept Chem, College Stn, TX 77843 USA; [Swennenhuis, Bert H. G.; Bengali, Ashfaq A.] Texas A&M Univ Qatar, Dept Chem, Doha, Qatar; [Fan, Wai Yip] Natl Univ Singapore, Dept Chem, Singapore 117543, Singapore
Reprint Address:  Darensbourg, DJ, Texas A&M Univ, Dept Chem, College Stn, TX 77843 USA.
Funding Agency:  Qatar National Research Fund
Publisher:  AMER CHEMICAL SOC
Publisher Address:  1155 16TH ST, NW, WASHINGTON, DC 20036 USA
ISSN:  0020-1669
29-char Source Abbrev.:  INORG CHEM
ISO Source Abbrev.:  Inorg. Chem.
Subject Category:  Chemistry, Inorganic & Nuclear
ISI Document Delivery No.:  634LM
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