10.1021/om300759p.s001
Joachim Ballmann
Joachim
Ballmann
Fraser Pick
Fraser
Pick
Ludovic Castro
Ludovic
Castro
Michael D. Fryzuk
Michael D.
Fryzuk
Laurent Maron
Laurent
Maron
Cleavage of Carbon Monoxide
Promoted by a Dinuclear
Tantalum Tetrahydride Complex
American Chemical Society
2012
transition states
DFT calculations
PhP
Carbon Monoxide Promoted
CH 4.
CO
dinuclear tetrahydride
carbon monoxide
NPN
analysis
Dinuclear Tantalum Tetrahydride ComplexThe reaction
2012-12-24 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Cleavage_of_Carbon_Monoxide_Promoted_by_a_Dinuclear_Tantalum_Tetrahydride_Complex/2457553
The reaction of one equivalent of carbon monoxide with
the dinuclear
tetrahydride complex ([NPN]Ta)<sub>2</sub>(μ-H)<sub>4</sub> (where
NPN = PhP(CH<sub>2</sub>SiMe<sub>2</sub>NPh)<sub>2</sub>) results
in the cleavage of the CO triple bond and formation of ([NPN]Ta)(μ-O)(μ-H)(Ta[NPN′])
(where NPN′ = PhP(CH<sub>2</sub>SiMe<sub>2</sub>NPh)(CH<sub>2</sub>SiMe<sub>2</sub>NC<sub>6</sub>H<sub>4</sub>)) via extrusion
of CH<sub>4</sub>. The identity of the ditantalum complex was confirmed
by single-crystal X-ray analysis, isotopic labeling studies, and GC-MS
analysis of the methane released. DFT calculations were performed
to provide information on the initial adduct formed and likely transition
states for the process.