Rhenium–silver bicyclic “spiro” hydrido-carbonyl clusters: NMR investigation of their formation and reversible fragmentation

• Polynuclear hydrido complexes able to act as chelating bidentate ligands towards Ag+.
• Formation of bicyclic Re–Ag clusters, isolobal analogs of spiro hydrocarbons.
• Unprecedented spiro[4,4]nonane and spiro[2,4]heptane Re–Ag hydrido-carbonyl clusters.
• Ingress/egress of Re2 moieties, reversibly transforming pentametallic into trimetallic cycles.
• Intermolecular exchange of dinuclear and tetranuclear metal fragments.

The reactions of the hydrido complexes [Re2H2(μ-H)(CO)8]− (1) and [Re4H2(μ-H)3(CO)16]− (2) with 0.5 equivalents of AgOTf (OTf− = CF3SO3−) afforded rapidly and selectively the novel cluster anions [Ag(μ-H)4{Re2(μ-H)(CO)8}2]− (3) and [Ag(μ-H)4{Re4(μ-H)3(CO)16}2]− (4), respectively, formed by donor–acceptor interactions between the rhenium hydrides and the Ag+ cation. 1H and 109Ag NMR spectroscopies showed that each Ag atom is surrounded by four hydrido ligands, bridging Re–Ag interactions. The Re2AgRe2 cluster 3 therefore adopts the well known "bow-tie" geometry, constituted by two triangular clusters sharing the Ag vertex (spiro bis-cyclopropane). The Re4AgRe4 anion 4 has instead an unprecedented spiro bis-cyclopentane-like structure, which is stable in solution only at temperatures lower than 220 K. The NMR investigation of the behavior in solution of these complexes revealed different intra- and inter-molecular dynamic processes, involving reversible fragmentation of the cyclic structures, with elimination of neutral or anionic hydrido-carbonyl fragments and interconversion among the different spiro derivatives. In particular, at temperature higher than 220 K the onset of a dissociative equilibrium was observed, involving the egress of a Re2(μ-H)2(CO)8 fragment from 4, with formation of the [Ag(μ-H)4{Re2(μ-H)(CO)8}{Re4(μ-H)3(CO)16}]− anion 5, with a mixed spiro cyclopropane–cyclopentane-like structure, never previously observed. The fragmentation reaction was completely reversible on lowering the temperature. The mixed spiro derivative 5 was obtained (in mixture with the two symmetrical spiro derivatives 3 and 4) by either adding 1 equivalent of [Re2(μ-H)2(CO)8] to 3, or by reacting 1 equivalent of Ag+ with a 1:1 mixture of the free hydrido complexes 1 and 2. Intermolecular exchanges between the Re4H5 fragments of 4 and 5, and between the Re2H3 fragments of 3 and 5 were revealed by 2D 1H EXSY NMR experiments, which also showed exchange between the spiro bis-cyclopropane 3 and the free hydrido complex 1. Furthermore, a higher binding ability towards Ag+ of 1 with respect to 2 was proved, since 1 was found to be able to displace 2 from the spiro bis-cyclopentane adduct 4 and from the mixed spiro cyclopropane–cyclopentane 5, leading to free hydrido complex 2 and the spiro bis-cyclopropane 3.

1H and 109Ag NMR spectroscopies have shown that di- and tetra-nuclear polyhydrido anionic complexes of rhenium act as chelating "ligands" towards Ag+, affording penta-, hepta-, or nona-nuclear bicyclic structures, isolobal analogs of spiro hydrocarbons, which interconvert by reversible ingress/egress of [Re2(μ-H)2(CO)8] units.Figure optionsDownload as PowerPoint slide