Twinned versus linked organometallics - bimetallic “half-baguette” pentalenide complexes of Rh(i)

The application of Mg[Ph4Pn] and Li·K[Ph4Pn] in transmetalation reactions to a range of Rh(I) precursors led to the formation of “half-baguette” anti-[RhI(L)n]2[μ:η5:η5Ph4Pn] (L = 1,5-cyclooctadiene, norbornadiene, ethylene; n = 1, 2) and syn-[RhI(CO)2]2[μ:η5:η5Ph4Pn] complexes as well as the related iridium complex anti-[IrI(COD)]2[μ:η5:η5Ph4Pn]. With CO exclusive syn metalation was obtained even when using mono-nuclear Rh(I) precursors, indicating an electronic preference for syn metalation. DFT analysis showed this to be the result of π overlap between the adjacent M(CO)2 units which overcompensates for dz2 repulsion of the metals, an effect which can be overridden by steric clash of the auxiliary ligands to yield anti-configuration as seen in the larger olefin complexes. syn-[RhI(CO)2]2[μ:η5:η5Ph4Pn] is a rare example of a twinned organometallic where the two metals are held flexibly in close proximity, but the two d8 Rh(I) centres did not show signs of M–M bonding interactions or exhibit Lewis basic behaviour as in some related mono-nuclear Cp complexes due to the acceptor properties of the ligands. The ligand substitution chemistry of syn-[RhI(CO)2]2[μ:η5:η5Ph4Pn] was investigated with a series of electronically and sterically diverse donor ligands (P(OPh)3, P(OMe)3, PPh3, PMe3, dppe) yielding new mono- and bis-substituted complexes, with E-syn-[RhI(CO)(P{OR})3]2[μ:η5:η5Ph4Pn] (R = Me, Ph) characterised by XRD.