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Title: Three-Fold Intramolecular Ring Closing Alkene Metatheses of Square Planar Complexes with cis Phosphorus Donor Ligands P(X(CH 2 ) m CH═CH 2 ) 3 (X = −, m = 5–10; X = O, m = 3–5): Syntheses, Structures, and Thermal Properties of Macrocyclic Dibridgehead Diphosphorus Complexes
Award ID(s):
1153085 1566601
Author(s) / Creator(s):
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Date Published:
Journal Name:
Journal of the American Chemical Society
Page Range / eLocation ID:
8463 to 8478
Medium: X
Sponsoring Org:
National Science Foundation
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  1. Abstract

    Reactions of the IrVhydride [MeBDIDipp]IrH4{BDI=(Dipp)NC(Me)CH(Me)CN(Dipp); Dipp=2,6‐iPr2C6H3} with E[N(SiMe3)2]2(E=Sn, Pb) afforded the unusual dimeric dimetallotetrylenes ([MeBDIDipp]IrH)2(μ2‐E)2in good yields. Moreover, ([MeBDIDipp]IrH)2(μ2‐Ge)2was formed in situ from thermal decomposition of [MeBDIDipp]Ir(H)2Ge[N(SiMe3)2]2. These reactions are accompanied by liberation of HN(SiMe3)2and H2through the apparent cleavage of an E−N(SiMe3)2bond by Ir−H. In a reversal of this process, ([MeBDIDipp]IrH)2(μ2‐E)2reacted with excess H2to regenerate [MeBDIDipp]IrH4. Varying the concentrations of reactants led to formation of the trimeric ([MeBDIDipp]IrH2)3(μ2‐E)3. The further scope of this synthetic route was investigated with group 15 amides, and ([MeBDIDipp]IrH)2(μ2‐Bi)2was prepared by the reaction of [MeBDIDipp]IrH4with Bi(NMe2)3or Bi(OtBu)3to 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 Ir2E2(E=Sn, Pb) compounds characterized them as open‐shell singlets with confined nonbonding lone pairs at the E centers. In contrast, Ir2Bi2is characterized as having a closed‐shell singlet ground state.

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