Orientation of trimethylolethane cyclic phosphite in rhodium complexes : structure of [Rh(CH3COCHCOCH3)(CO)(P(OCH2)3CCH3)]
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Date
Authors
Van Rooyen, Petrus H.
Conradie, Jeanet
Journal Title
Journal ISSN
Volume Title
Publisher
Elsevier
Abstract
Density functional theory calculations showed that rotation of the (P(OCH2)3CCH3) group in the
rhodium-acetylacetonato complex [Rh(acac)(CO)(P(OCH2)3CCH3)] has a negligible influence on
the energy of the complex. Density functional theory calculations further showed that the minimum
energy orientation of the cyclic (P(OCH2)3CCH3) group in square planar rhodium-
(P(OCH2)3CCH3)-(CO) complexes containing a bidentate ligand that is larger than the
acetylacetonato ligand, is with one of the P-O bonds near parallel (within 10°) to the plane defined
by the four atoms coordinated to Rh. The three P-O bonds of the rigid (P(OCH2)3CCH3) group
adopt a C3-symmetrical conformation around the Rh-P axis. The lowest energy geometry of
[Rh(BID)(CO)(P(OCH2)3CCH3)] (BID = bidentate ligand with two O donor atoms and charge -1)
complexes is where one P-O bond is aligned near parallel to the Rh-OBID trans to CO bond, while the
geometry with a P-O bond orientated near parallel to the Rh-CCO bond, is slightly higher in energy,
but still possible experimentally. The highest energy orientation of the (P(OCH2)3CCH3) group in
square planar [Rh(BID)(CO)(P(OCH2)3CCH3)] complexes, is with one of the P-O bonds near
perpendicular to the plane described by the four atoms coordinated to Rh. The orientation of the
cyclic (P(OCH2)3CCH3) group in available experimental structures of square planar [Rh(BID)(CO)
(P(OCH2)3CCH3)] complexes, confirms this finding.
Description
Keywords
Structure, Cyclic phosphite, Rhodium-acetylacetonato complex, Density functional theory (DFT), Rhodium, β-Diketone
Sustainable Development Goals
Citation
Van Rooyen, PH & Conradie, J 2016, 'Orientation of trimethylolethane cyclic phosphite in rhodium complexes : structure of [Rh(CH3COCHCOCH3)(CO)(P(OCH2)3CCH3)]', Polyhedron, vol. 111, pp. 161-166.