Phosphinoamido ligand supported heterobimetallic rare-earth metal–palladium complexes: versatile structures and redox reactivities

Abstract

Heterobimetallic Ln(III)-Pd(0) complexes (Ln = Y, Sm, Gd, Yb) featuring tetranuclear structures with COD as bridges were obtained via the metallation of tris(phosphinoamido) rare-earth metal complexes [Ph2PNAd]3Ln (Ad = admantyl)...

Structure and bonding patterns in heterometallic organometallics with linear Ln–Pd–Ln motifs

“…39 Most reports of Ln–Pd interactions in the literature are larger than 3 Å, 33 with two notable exceptions: the Pd–Lu and Pd–Y series of compounds published by Roesky and co-workers, 30 in which the reported metal–metal distances are 2.9031(11) Å, 2.9712(8) Å and 2.9898(6) Å and the series of Ln–Pd phosphinoamido complexes with Ln–Pd (Ln = Sc, Y, Sm, Yb, Gd, Lu) distances ranging from 2.432(2) to 2.862(3) Å that have been reported by Cui and co-workers. 51–53 It is worth noting that a shorter Pd–U distance of 2.69 Å was reported, in which a covalent interaction was suggested. 54 A feature that merits attention is that the Ln–Pd distances in 4 and 5 differ by only 0.017 Å, significantly smaller than the 0.11 Å difference of the covalence radii between both lanthanide ions.…”

“…60 The Pd is in the +II oxidation state with one Cp* ring coordinated and an intermetallic Pd–Yb distance of 2.8766(3) Å is reported. The distance can be compared with the short reported Pd–Yb distances of 2.7879(6) Å 51,53 and 2.8397(4) Å. 52…”

Recent advances in heterometallic clusters with f-block metal–metal bonds: synthesis, reactivity and applications

“…68 In addition, complexes 74 and 75 could react with disulphide PhSSPh, which lead to the S–S bond cleavage. 69 The Pd(0) center was proposed to play a role as electron reservoir, a possible oxidative addition and rearrangement of PhSSPh in RE–Pd occurred and afforded complexes 77 and 78 , respectively.…”

Heterometallic bond activation enabled by unsymmetrical ligand scaffolds: bridging the opposites

“…Mixed phosphine/amide P,N-donor ligands have been widely used to selectively form heterobimetallic compounds with polarized metal–metal bonds, typically between late TM and an early TM or rare-earth (RE) element. 91,92 For example, Lu and co-workers reported a series of bimetallic Ni 0 complexes with Ga III or trivalent rare-earth (RE) metals 93 (Scheme 21). Two synthetic approaches were used to build a bimetallic core: in the case of Ga complex 3.19d , the phosphine-bound Ni 0 complex with lithiated ligand was obtained first, followed by treatment with GaCl 3 , while in case of Ni/RE pair, a rare-earth containing metalloligand 3.17 was first obtained, which was then metalated with a Ni 0 precursor.…”