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Creators/Authors contains: "Tilley, T_Don"

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  1. ; ; ; ; ; (, Chemistry – A European Journal)
    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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  2. ; ; ; ; ; ; ; ; (, Chemistry – A European Journal)
    Abstract Anionic molecular models for nonhydrolyzed and partially hydrolyzed aluminum and gallium framework sites on silica, M[OSi(OtBu)3]4−and HOM[OSi(OtBu)3]3−(where M=Al or Ga), were synthesized from anionic chlorides Li{M[OSi(OtBu)3]3Cl} in salt metathesis reactions. Sequestration of lithium cations with [12]crown‐4 afforded charge‐separated ion pairs composed of monomeric anions M[OSi(OtBu)3]4−with outer‐sphere [([12]crown‐4)2Li]+cations, and hydroxides {HOM[OSi(OtBu)3]3} with pendant [([12]crown‐4)Li]+cations. These molecular models were characterized by single‐crystal X‐ray diffraction, vibrational spectroscopy, mass spectrometry and NMR spectroscopy. Upon treatment of monomeric [([12]crown‐4)Li]{HOM[OSi(OtBu)3]3} complexes with benzyl alcohol, benzyloxide complexes were formed, modeling a possible pathway for the formation of active sites for Meerwin–Ponndorf–Verley (MPV) transfer hydrogenations with Al/Ga‐doped silica catalysts. 
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