Open Access Repository

Breaking chemistry's strongest bond: can three-coordinate [M{N(R)Ar}3] complexes cleave carbon monoxide


Downloads per month over past year

Christian, G, Stranger, R, Petrie, S, Yates, BF and Cummins, CC 2007 , 'Breaking chemistry's strongest bond: can three-coordinate [M{N(R)Ar}3] complexes cleave carbon monoxide' , Chemistry: A European Journal, vol. 13, no. 15 , pp. 4264-4272 , doi: 10.1002/chem.200601643.

[img] PDF
3815.pdf | Request a copy
Full text restricted
Available under University of Tasmania Standard License.


The reaction pathway for the
interaction of CO with three-coordinate
TaIII, WIII and ReIII complexes
(modelled on the experimental [M{NACHTUNGTRENUNG(
tBu)Ar}3] system) has been explored
by using density functional methods.
Calculations show that CO binds without
a barrier to [ReACHTUNGTRENUNG(NH2)3], forming
the encounter complex [OCRe-
ACHTUNGTRENUNG(NH2)3], which is stabilized by
280 kJmol1 relative to the reactants.
The binding of [TaACHTUNGTRENUNG(NH2)3] to the
oxygen terminus of CO is inhibited by
a barrier of only 20 kJmol1 and is followed
by spontaneous cleavage of the
CO bond to form the products [C
features of the potential energy
surface are more favourable to CO
cleavage than the analogous N2 cleavage
by [MoACHTUNGTRENUNG(NH2)3], which is less exothermic
(335 vs. 467 kJmol1) and is
impeded by a significant barrier
(66 kJmol1). The ReIII/TaIII/CO system
therefore appears to be an excellent
candidate for cleaving the exceptionally
strong CO bond under mild laboratory
conditions. The related WIII/TaIII
dimer, which significantly weakens but
does not cleave the CO bond, may be a
suitable alternative when the chemistry
is to be performed on activated CO
rather than on the strongly bound
oxide and carbide cleavage products.

Item Type: Article
Authors/Creators:Christian, G and Stranger, R and Petrie, S and Yates, BF and Cummins, CC
Keywords: CO activation · density functional calculations · rhenium · tantalum · threecoordinate complexes
Journal or Publication Title: Chemistry: A European Journal
Publisher: Wiley-VCH
ISSN: 0947-6539
DOI / ID Number: 10.1002/chem.200601643
Additional Information:

The original publication is available at

Item Statistics: View statistics for this item

Actions (login required)

Item Control Page Item Control Page