Rhodium-rhodium interactions in [Rh(β-diketonato)(CO)2] complexes

Abstract

Synopsis Highlights Crystal structures of [Rh(R1COCHCOR2)(CO)2], where R1, R2 = CF3, C4H3S or Ph Metallophilic rhodium-rhodium interactions in the solid state Sigma-sigma interaction of dz2 molecular orbitals AIM bonding paths NBO LP(Rh dz2)-LP*(Rh pz) interaction

Multinuclear rhodium complexes supported by tetra-tert-butoxy disiloxide ligand: synthesis, structure, and reactivity

“…The distance between Rh2 and Rh2 0 is 3.3674(3) Å, which is within typical distances indicating Rh-Rh interaction (3.18-3.54 Å). [49][50][51][52][53][54][55] Indeed, Conradie et al reported that square-planar rhodium carbonyl complexes such as [(CO) 2 Rh(acac)] (acac = acetylacetonate) formed intermolecular rhodium chains by weak Rh-Rh interactions in a crystal packing system. [52][53][54][55] NMR analysis showed that the bis-dinuclear structure of 4 in the crystal structure should be maintained in the solution state.…”

“…[49][50][51][52][53][54][55] Indeed, Conradie et al reported that square-planar rhodium carbonyl complexes such as [(CO) 2 Rh(acac)] (acac = acetylacetonate) formed intermolecular rhodium chains by weak Rh-Rh interactions in a crystal packing system. [52][53][54][55] NMR analysis showed that the bis-dinuclear structure of 4 in the crystal structure should be maintained in the solution state. In the 13 C NMR spectrum, the signals derived from carbonyl groups coordinated to the Rh centers were observed at 181.7 ppm ( 1 J C-Rh = 74.7 Hz) and 181.3 ppm ( 1 J C-Rh = 74.4 Hz), which is consistent with the fact that Rh1 and Rh2 are non-equivalent in the solid state.…”

Single Crystal X-ray Diffraction Studies of Two Polymorphic Modifications of the Dicarbonyl-o-Semiquinonato Rhodium Complex at Different Temperatures. Destruction Stimulated by Cooling Versus Stability

“…This sample did not detect photomechanical properties. Later, the number of structural analogues of complex 1 having substituents in 4,5-positions of the semiquinonato ligand was synthesized and characterized by our group , and Prof. Mitsumi. − It should be noted that different [Rh­(β-diketonato)­(CO) 2 ] complexes are also capable to form both dimer pairs − and 1-D coordination polymers − in the crystalline state. Some of them display interesting magnetic properties and electric conductivity.…”

Kinetic‐Mechanistic and Solid‐State Study of the Oxidative Addition and Migratory Insertion of Iodomethane to [Rhodium(S,O‐BdiPT or N,O‐ox)(CO)(PR1R2R3)] Complexes

“…In the Monsanto process the metal carbonyl species is [Rh I ( I ) 2 (CO) 2 ] – , which is relatively unstable. Rhodium carbonyl species containing phosphine ligands and/or bidentate ligands are generally found to be more stable, although some interesting recent metallophilic interactions have been described in Rh I dicarbonyl complexes . Furthermore, by tuning the stereo‐electronic properties of these ligands, the carbonylation process is directed towards different outcomes.…”