FLP-type nitrile activation and cyclic ether ring-opening by halo-borane nonagermanide-cluster Lewis acid-base pairs.

ABSTRACT: Even though homoatomic nine-atom germanium clusters are known for two decades, their chemical properties are still rarely investigated. We now discovered that Zintl ion main group-element clusters possess a reactive lone pair of electrons, and we show a new pathway to bind ligands with functional groups to the [Ge₉] cluster core through Ge-C bond formation. We report on the reactivity of [Ge₉{Si(TMS)₃}₂]^2- (TMS = trimethylsilyl) towards a series of Lewis acidic bromo-boranes. The reaction of [Ge₉{Si(TMS)₃}₂]^2- and DAB ^o-tol-Br (DAB = 1,3,2-diazaborolidine; o-tol = 2-methylphenyl) resulted, depending on the reaction protocol, either in the formation of [Ge₉{Si(TMS)₃}₂DAB ^o-tol]^- (1a) with direct Ge-B interactions, or in [Ge₉{Si(TMS)₃}₂(CH₂)₄O-DAB ^o-tol]^- (2a) featuring a ring-opened thf moiety. Ring opening reactions occur for all bulkier DAB^R-Br [R: o-xyl (2,6-dimethylphenyl), Mes (2,4,6-trimethylphenyl), Dipp (2,6-diisopropylphenyl)], DAB(ii)^Dipp-Br and acyclic ( ⁱ Pr₂N)₂BBr without Ge-B bond formation as shown for the structural characterization of the ring-opened products of thf (3, 4) and trimethylene oxide (5). In contrast to thf, the activation of CH₃CN requires the simultaneous presence of Lewis-acid and Lewis-basic reactants allowing the formation of [Ge₉{Si(TMS)₃}₂CH₃C[double bond, length as m-dash]N-DAB^Mes]^- (6a). Within the presented compounds, 3 and 4 show an unusual substitution pattern of the three ligands at the [Ge₉] core in the solid state. The [Ge₉] cluster/borane systems correspond to intermolecular frustrated Lewis pairs (FLPs), in which the [Ge₉] cluster with several lone pairs represents the Lewis base, and the borane is the Lewis acid.

SUBMITTER: Wallach C 

PROVIDER: S-EPMC8153081 | biostudies-literature |

REPOSITORIES: biostudies-literature