The application of and in transmetalation reactions to a range of Rh(I) precursors led to the formation of "half-baguette" (L = 1,5-cyclooctadiene, norbornadiene, ethylene; = 1, 2) and complexes as well as the related iridium complex . With CO exclusive metalation was obtained even when using mono-nuclear Rh(I) precursors, indicating an electronic preference for metalation. DFT analysis showed this to be the result of π overlap between the adjacent M(CO) units which overcompensates for d repulsion of the metals, an effect which can be overridden by steric clash of the auxiliary ligands to yield -configuration as seen in the larger olefin complexes. is a rare example of a twinned organometallic where the two metals are held flexibly in close proximity, but the two Rh(I) centres did not show signs of M-M bonding interactions or exhibit Lewis basic behaviour as in some related mono-nuclear complexes due to the acceptor properties of the ligands. The ligand substitution chemistry of was investigated with a series of electronically and sterically diverse donor ligands (P(OPh), P(OMe), PPh, PMe, dppe) yielding new mono- and bis-substituted complexes, with (R = Me, Ph) characterised by XRD.
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