Aryl compounds of rhodium: syntheses and X-ray crystal structures

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

“…In the case of [Rh II (2,4,6-i-PrC 6 H 2 ) 2 (tht) 2 ] a new EPR spectrum was obtained after addition of CO. At 77 K, it consists of several signals with g $ 2, which suggest that the unpaired electron is located at the (coordinated) CO ligand. Removal of all volatiles resulted in regeneration of [Rh II (2,4,6-i-PrC 6 H 2 )(tht) 2 ], which indicates that coordination of CO is reversible (27). In contrast to the previous examples, in this case no decomposition to a Rh(I) species upon release of an aryl radical takes place.…”

“…The large g anisotropies (Table III) are consistent with the proposed electronic structures, with the unpaired electron mainly residing in a d xy or d z 2 orbital (with the z axis perpendicular to the coordination plane of rhodium). The EPR spectrum of [Rh II (2,4,6-i-PrC 6 H 2 )(tht) 2 ] shows coupling of the unpaired electron to the 103 Rh (I ¼ ½) nucleus at all three g values (Table III) (27). For all other complexes, no resolved (super)hyperfine structures were observed.…”

14-Electron Four-Coordinate Ru(II) Carbyl Complexes and Their Five-Coordinate Precursors: Synthesis, Double Agostic Interactions, and Reactivity

“…31 P{ 1 H}-NMR: 41.0 (d, JPF ) 22 Hz). 19 F NMR: -201 (tq, JPF ) 22 Hz, JFH ) 4 Hz, Ru-F). IR (C6D6): 1887 (ν(CO)).…”

“…31 P{ 1 H} NMR (121 Hz, C6D6, 20°C): 42.0 (d, JPF ) 24 Hz, Ru-P). 19 F NMR (376 MHz, C6D6, 20°C): -204.5 (t, J ) 24 Hz, Ru-F). IR (C6D6, cm -1 ): ν(CO) ) 1890.…”

Synthesis of the homoleptic rhodium(III) complex [Rh(C6Cl5)3]. Molecular structures of [Rh(C6Cl5)3] and [Rh(C6Cl4–C6Cl4)(C6Cl5)(SC4H8)2]

“…10 On the other hand, the preparation of aryl derivatives can be achieved by the reaction of the appropriate halogen starting metal complex with aryl-lithium or -magnesium compounds, but these reactions are very sensitive to the chosen conditions. For instance, the nature and yield of the products of the reactions of [RhCl 3 (tht) 3 ] (tht = tetrahydrothiophene) with lithium derivatives depends on the experimental conditions and on the steric properties of the aryl or alkyl group used; so an excess of LiC 6 Cl 5 leads 10 to the preparation of the arylated rhodium() dianion [Rh(C 6 Cl 5 ) 4 ] 2Ϫ and with Li(2,4,6-i Pr 3 C 6 H 2 ) yields 11 the neutral square-planar complex [Rh (2,4,6-…”