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Scission of Carbon Monoxide Using TaR3, R = (N(tBu)Ph) or OSi(tBu)3: a DFT Investigation

journal contribution
posted on 2023-05-17, 04:59 authored by Brookes, NJ, Alireza AriafardAlireza Ariafard, Stranger, R, Brian YatesBrian Yates
The experimentally known reduction of carbon monoxide using a 3-coordinate [Ta(silox)3] (silox = OSi-(tBu)3) complex initially forms a ketenylidene [(silox)3Ta-CCO], followed by a dicarbide [(silox)3Ta-CC-Ta-(silox)3] structure. The mechanism for this intricate reaction has finally been revealed by using density functional theory, and importantly a likely structure for the previously unknown intermediate [(silox)3Ta-CO]2 has been identified. The analysis of the reaction pathway and the numerous intermediates has also uncovered an interesting pattern that results in CO cleavage, that being scission from a structure of the general form [(silox)3Ta-C nO] in which n is even. When n is odd, cleavage cannot occur. The mechanism has been extended to consider the effect of altering both the metal species and the ligand environment. Specifically, we predict that introducing electron-rich metals to the right of Ta in the periodic table to create mixed-metal dinuclear intermediates shows great promise, as does the ligand environment of the Cummins-style 3-coordinate amide structure. This latter environment has the added complexity of improved electron donation from amide rotation that can significantly increase the reaction exothermicity. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Funding

Australian Research Council

History

Publication title

Chemistry: A European Journal

Volume

16

Issue

27

Pagination

8117-8132

ISSN

0947-6539

Department/School

School of Natural Sciences

Publisher

Wiley-V C H Verlag Gmbh

Place of publication

Po Box 10 11 61, Weinheim, Germany, D-69451

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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