Polarized Au(i)/Rh(i) bimetallic pairs cooperatively trigger ligand non-innocence and bond activation

Abstract

The combination of molecular metallic fragments of contrasting Lewis character offers many possibilities for cooperative bond activation and for the disclosure of unusual reactivity. Here we provide a systematic investigation...

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

“…Related mononuclear four-coordinate d 8 complexes are known to display nucleophilic behaviour by virtue of their filled, non-bonding d z 2 orbital which may act as a σ-donor to a range of Lewis acids. 78 This effect has even been seen (and exploited for intermetallic reactivity in metal-based Lewis pairs 79–82 ) in formally five-coordinate 18 electron η 5 -CpRh( i ) complexes that have an empty, non-bonding d z 2 orbital, 79 where their nucleophilic behaviour may either arise from an electron-rich Rh–L bond or a temporary η 5 –η 3 slip of the Cp ligand. However, addition of AlCl 3 to anti - 3 and syn - 5 in THF showed no changes in their 1 H NMR spectra even after one week at room temperature.…”

Ligand Postsynthetic Functionalization with Fluorinated Boranes and Implications in Hydrogenation Catalysis

“…In the context of ligand post-synthetic functionalization, we recently disclosed a reversible Cp* to metal hydride migration in compound [(η 5 -C 5 Me 5 )­Rh­(PMe 3 ) 2 ] upon addition of bulky Au­(I) fragments with concomitant formation of new (Cp*)­CH 2 –Au bonds . In contrast, ligand C–H bond activation does not take place for the related indenyl compound [(η 5 -C 9 H 7 )­Rh­(PPh 3 ) 2 ] ( 1 ), where we could only detect the formation of Rh → Au bimetallic adducts . Bearing in mind the high electrophilicity of perfluorinated boranes, we hypothesized that those could succeed in the direct functionalization of the indenyl ligand in 1 and thus provide facile access to bifunctional complexes with catalytic potential.…”

Cooperative activation of carbon–hydrogen bonds by heterobimetallic systems

“…81,82 Dalton Transactions Perspective the basicity of the phosphines bound to Rh also play an important role in these Cp* non-innocent behaviour. 82…”

“…18 Reversible CH 3 hydride migration to Rh promoted promoted by electrophilic gold fragments. 81,82 Dalton Transactions Perspective the basicity of the phosphines bound to Rh also play an important role in these Cp* non-innocent behaviour. 82…”