Conformation analysis of triphenylphosphine in trans and cis triphenylphosphine-substituted Fischer carbene complexes
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Date
Authors
Landman, Marile
Levell, Tamzyn J.
Van Rooyen, Petrus H.
Conradie, Jeanet
Journal Title
Journal ISSN
Volume Title
Publisher
Elsevier
Abstract
The synthesis and selected crystal structures of novel (M = Cr or Mo) and known (M =W) [(CO)4(PPh3)
M = C(OEt)R] complexes, M = Cr, R = 2-thienyl (1), 2-furyl (2); M = Mo, R = 2-thienyl (3), 2-furyl (4);
M = W, R = 2-thienyl (5), 2-furyl (6), are presented. Experimental crystal structures and DFT calculations
of selected trans- and cis-triphenylphosphine-substituted Fischer carbene complexes, illustrate that the
minimum energy conformation of triphenylphosphine (PPh3) in octahedral [(CO)4(PPh3)ML]-complexes
generally have distinct features that can be described in terms of the ‘‘plane of nadir energy’’, a plane
linking all points of minimum steric compression between the ligands. The generally observed orientation
of PPh3 involves a correlated feathering of the phenyl groups with the PACipso bond of one phenyl
group orientated near parallel to the nadir plane, and a meta carbon (Cm) of the other two phenyl groups
orientated as near as possible to the nadir plane, orthogonal to the first. Although the orientation of PPh3
in 6-trans, [(CO)4(PPh3)W = C(OEt)2-furyl], deviates from this, DFT correctly calculated the unexpected
and not generally observed PPh3 orientation.
Description
Keywords
Fischer carbene, Phosphine, Conformational analysis, Density functional theory (DFT)
Sustainable Development Goals
Citation
Landman, M, Levell, T, Van Rooyen, PH & Conradie, J 2014, 'Conformation analysis of triphenylphosphine in trans and cis triphenylphosphine-substituted Fischer carbene complexes', Journal of Molecular Structure, vol. 1065-1066, no. 1, pp. 29-38.