On the mechanisms of degenerate ligand exchange in [M(CH(3))](+)/CH(4) Couples (M=Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) as explored by mass spectrometric and computational studies: oxidative addition/reductive elimination versus sigma-complex-assisted metathesis

Chemistry : a European Journal
Marc ArmélinH Schwarz

Abstract

The degenerate ligand exchange in [M(CH(3))](+)/CH(4) couples occurs in the gas phase at room temperature for M=Ni, Ru, Rh, Pd, and Pt, whereas the complexes containing Fe and Co are unreactive. Details of hydrogen-atom scrambling versus direct ligand switch have been uncovered by labeling experiments with CD(4) and (13)CH(4), respectively. The reactivity scale ranges from unreactive (M=Fe, Co) or inefficient (M=Ni, Pd) to moderately (M=Ru) and rather reactive (M=Rh, Pt). Quite extensive, but not complete, H/D exchange between the hydrogen atoms of the incoming and outgoing methyl groups is observed for M=Pt, whereas for M=Ni and Pd a predominantly direct ligand switch prevails. DFT calculations performed at the B3LYP level of theory account well for the thermal nonreactivity of the Fe and Co couples. For [Ni[CH(3))](+)/CH(4), a sigma-complex-assisted metathesis (sigma-CAM) is operative such that, in a two-state reactivity (TSR) scenario, two spin flips between the (3)A ground and (1)A excited states take place at the entrance and exit channels of the encounter complexes. For M=Ru and Rh, only oxidative addition/reductive elimination (OA/RE) is favored energetically, and the reaction is confined to the electronic ground states ...Continue Reading

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Citations

May 4, 2010·Journal of the American Society for Mass Spectrometry·Jing ZhouYinlong Guo
Oct 23, 2015·Chemistry : a European Journal·Zi-Yu LiJiannian Yao
Nov 19, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Maria Schlangen, Helmut Schwarz
Dec 4, 2009·Chemistry : a European Journal·Mahiuddin BaidyaHerbert Mayr
Sep 11, 2010·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Oier LakuntzaJesus M Ugalde
Jan 26, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Robert KretschmerHelmut Schwarz
Jun 10, 2011·Angewandte Chemie·Helmut Schwarz
Jan 31, 2018·Physical Chemistry Chemical Physics : PCCP·Qiang ChenSheng-Gui He
Jan 1, 2010·Chemical Reviews·Jana Roithová, Detlef Schröder
Mar 3, 2012·The Journal of Physical Chemistry. a·Lianming ZhaoWenyue Guo
Aug 16, 2012·The Journal of Physical Chemistry. a·Alexandra TsybizovaTibor András Rokob
Feb 2, 2011·Journal of the American Chemical Society·James A CalladineKhuong Q Vuong

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