Organometallics p. 1957 - 1966 (1988)
Update date:2022-09-26
Topics:
Van Der Zeijden, Adolphus A. H.
Van Koten, Gerard
Nordemann, Richard A.
Koji?-Prodi?, Biserka
Spek, Anthony L.
The reaction of Lin[C6H3(CH2NMe 2)-o-R-o′]n with [RhCl(diene)]2 yields the ortho-chelated arylrhodium(I) complexes Rh[C6H3(CH2NMe 2)-o-R-o′](diene) (R = CH2NMe2, diene = COD (1a) or NBD (1b); diene = COD, R = Me (2) or H (3)). The solid-state structure of 1a was determined by a single-crystal X-ray diffraction study. C20H31N2Rh: triclinic, space group P1, with lattice parameters a = 10.169 (1) ?, b = 13.036 (1) ?, c = 14.688 (2) ?, α = 79.54 (1)°, β = 77.04 (1)°, γ = 79.53°; V = 1845.6 (4) ?3, Z = 4; D(calcd) = 1.448 g cm-3. Refinement with 4696 observed reflections converged at R = 0.0395. The structure of 1a consists of a rhodium(I) center that has a square-planar coordination comprising the two double bonds of COD and a C atom and one of the N atoms of the monoanionic aryl ligand. In solution compounds 1 and 2 exhibit dynamic behavior which involves a reversible dissociation of the Rh-N bond and rotation of the aryl moiety around Rh-C. This process, which generates a highly unsaturated T-shaped 14 electron species, is accompanied by the relief of steric repulsions within the complex. Complex 1 reacts with a range of electrophilic reagents leading to Rh-C bond breakage (HX, X = acac, Cl, Br, OAc, OH, OMe, L-alanyl; MXnLm, SnMe2Br2, NiBr2(PBu3)2, ZrCl4, PdCl2(NCPh)2, HgCl2, PtBr2(COD), and [IrCl(COD)]2). A redox reaction of 1 with AgX (X = OAc, NO3) leads to the formation of RhIIIX2[C6H3(CH2NMe 2)2-o,o′](H2O).
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