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

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Christian, G and Stranger, R and Petrie, S and 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, 13 (15). pp. 4264-4272. ISSN 0947-6539

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Abstract

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
ReACHTUNGTRENUNG(NH2)3] and [OTaACHTUNGTRENUNG(NH2)3]. The salient
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
Keywords: CO activation · density functional calculations · rhenium · tantalum · threecoordinate complexes
Journal or Publication Title: Chemistry: A European Journal
Publisher: Wiley-VCH
Page Range: pp. 4264-4272
ISSN: 0947-6539
Identification Number - DOI: 10.1002/chem.200601643
Additional Information:

The original publication is available at
http://www.interscience.wiley.com/

Date Deposited: 07 Apr 2008 14:07
Last Modified: 18 Nov 2014 03:33
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