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Dimetalloylene (M-E-M) Complexes of Heavier Main Group Elements Ge, Sn, Pb, Bi via Cleavage of E-X Bonds (X=N(SiMe<sub>3</sub> )<sub>2</sub> , OtBu) with an Iridium Hydride.

ABSTRACT: Reactions of the IrV hydride [Me BDIDipp ]IrH4 {BDI=(Dipp)NC(Me)CH(Me)CN(Dipp); Dipp=2,6-iPr2 C6 H3 } with E[N(SiMe3 )2 ]2 (E=Sn, Pb) afforded the unusual dimeric dimetallotetrylenes ([Me BDIDipp ]IrH)2 (μ2 -E)2 in good yields. Moreover, ([Me BDIDipp ]IrH)2 (μ2 -Ge)2 was formed in situ from thermal decomposition of [Me BDIDipp ]Ir(H)2 Ge[N(SiMe3 )2 ]2 . These reactions are accompanied by liberation of HN(SiMe3 )2 and H2 through the apparent cleavage of an E-N(SiMe3 )2 bond by Ir-H. In a reversal of this process, ([Me BDIDipp ]IrH)2 (μ2 -E)2 reacted with excess H2 to regenerate [Me BDIDipp ]IrH4 . Varying the concentrations of reactants led to formation of the trimeric ([Me BDIDipp ]IrH2 )3 (μ2 -E)3 . The further scope of this synthetic route was investigated with group 15 amides, and ([Me BDIDipp ]IrH)2 (μ2 -Bi)2 was prepared by the reaction of [Me BDIDipp ]IrH4 with Bi(NMe2 )3 or Bi(OtBu)3 to afford the first example of a "naked" two-coordinate Bi atom bound exclusively to transition metals. A viable mechanism that accounts for the formation of these products is proposed. Computational investigations of the Ir2 E2 (E=Sn, Pb) compounds characterized them as open-shell singlets with confined nonbonding lone pairs at the E centers. In contrast, Ir2 Bi2 is characterized as having a closed-shell singlet ground state.

SUBMITTER: Saint-Denis TG 

PROVIDER: S-EPMC12285657 | biostudies-literature | 2023 Sep

REPOSITORIES: biostudies-literature

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Dimetalloylene (M-E-M) Complexes of Heavier Main Group Elements Ge, Sn, Pb, Bi via Cleavage of E-X Bonds (X=N(SiMe&lt;sub&gt;3&lt;/sub&gt; )&lt;sub&gt;2&lt;/sub&gt; , OtBu) with an Iridium Hydride.

Saint-Denis Tyler G TG   Zhang Bowen B   Settineri Nicholas S NS   Handford Rex C RC   Hall Michael B MB   Tilley T Don TD  

Chemistry (Weinheim an der Bergstrasse, Germany) 20230725 49

Reactions of the Ir<sup>V</sup> hydride [<sup>Me</sup> BDI<sup>Dipp</sup> ]IrH<sub>4</sub> {BDI=(Dipp)NC(Me)CH(Me)CN(Dipp); Dipp=2,6-iPr<sub>2</sub> C<sub>6</sub> H<sub>3</sub> } with E[N(SiMe<sub>3</sub> )<sub>2</sub> ]<sub>2</sub> (E=Sn, Pb) afforded the unusual dimeric dimetallotetrylenes ([<sup>Me</sup> BDI<sup>Dipp</sup> ]IrH)<sub>2</sub> (μ<sub>2</sub> -E)<sub>2</sub> in good yields. Moreover, ([<sup>Me</sup> BDI<sup>Dipp</sup> ]IrH)<sub>2</sub> (μ<sub>2</sub> -Ge)<sub>2</sub> was formed i  ...[more]

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