structure of [(3‐Me‐C6H4CN)2Na(TMEDA)2]+ [{6‐Zn(t‐...Scheme 2.24 Calculated two‐step mechanism for zincation of benzene with bisa...Scheme 2.25 Dimetallation of thiophene to form novel zincocycle 90.Scheme 2.26 Zincation of benzoylferrocene showing metallated intermediate 91Scheme 2.27 Zincation of THF with sodium zincate 94.Figure 2.18 Molecular structure of Zn[(μ‐OPiv)(μ‐Cl)Li(THF)]298.Scheme 2.28 ZnCl2 insertion into lithiated Dip‐dabqdi complex to yield bimet...Figure 2.19 Proposed anisolyl lithium zincate intermediates from theoretical...Figure 2.20 Postulated mechanism for catalytic hydroboration of carbonyl fun...Scheme 2.29 Synthesis and versatile reactivity of i‐Bu2Al(TMP)HLi 101....Figure 2.21 Molecular structure of (THF)Li(μ‐TMP)(μ‐i‐Bu)Ali‐Bu2Figure 2.22 Molecular structure of (THF)Li(μ‐TMP)(μ‐C4H7O)Ali‐Bu2103, ...Scheme 2.30 Basis of trans‐metal‐trapping using a lithium base and stericall...Figure 2.23 Molecular structures of polymeric lithiated NHC 104 (left), ring...Scheme 2.31 Nucleophilic addition of homoleptic lithium gallate to pyrazine....Figure 2.24 Molecular structures of mono‐metallated 109 and di‐metallated py...Figure 2.25 Molecular structures of aluminated fluoroanisole 111, lithium fl...Scheme 2.32 Contrasting reactivity of benzophenone with magnesium zincate 11...Scheme 2.33 Stoichiometric dependence on preparation of bimetallic Mg/Zn spe...Figure 2.26 Molecular structure of [(THF)4MgCl2Zn(t‐Bu)Cl] 116.Figure 2.27 Molecular structures of [{Mg(THF)6}2+ 2{Zn(o‐C6H4‐OMe)3}−]...Scheme 2.34 Co‐complexation of EtMgCl with ZnCl2 (120) and LiCl assisted add...Scheme 2.35 Heteronuclear complex 124 used in polymerization alongside propo...Figure 2.28 Molecular structure of Mg/Zn heterometallic polymerization catal...Scheme 2.36 Trapping of carbon dioxide units within a bimetallic Mg/Al compl...Figure 2.29 Molecular structure of [(Nacnac)Ca+(C6H6)2−AlIII(Nacnac)(CScheme 2.37 C–F activation of perfluorobenzene with subvalent M–M bonded spe...3 Chapter 3Scheme 3.1 Generalized representation of the Schlenk equilibrium and the mon...Scheme 3.2 Directed ortho‐metalation by organolithium reagents.Scheme 3.3 (a) Eaton’s magnesiation of a functionalized cubane and Kondo’s m...Figure 3.1 The structures of the organolithium magnesiate contact ion pairs,...Figure 3.2 The solid‐state structures of (a) Mulvey’s lithium magnesiate, co...Figure 3.3 The ‘inverse crown’ structures of (a) Na/Mg compound 9 and (b) K/...Scheme 3.4 Synthesis of the sodium magnesiate ‘inverse crowns’, compounds 9 ...Figure 3.4 (a) Fourfold deprotonation of ferrocene and (b) monodeprotonation...Scheme 3.5 Deprotonation of benzene and meta‐deprotonation of toluene by the...Scheme 3.6 ‘Cleave and capture’ of THF effected by the alkyl‐TMP sodium magn...Scheme 3.7 Kinetic and thermodynamic products, compounds 26 and 27, resultin...Figure 3.5 The tetrameric ‘pre‐inverse crown’, compound 28.Figure 3.6 The structures of the sodium‐magnesiate inverse crowns (a) compou...Scheme 3.8 Proposed methyllithium deaggregation equilibrium in the presence ...Scheme 3.9 Selective metalation of bromoarenes by the turbo‐Grignard reagent...Scheme 3.10 Applications of magnesium–halogen exchange and arene metalation ...Scheme 3.11 Use of the turbo‐Grignard system, i‐PrMgCl·LiCl, for the selecti...Scheme 3.12 Turbo‐Grignard mediated deprotonation of terminal alkynes and ox...Scheme 3.13 Use of the turbo‐Grignard system, i‐Pr‐MgCl·LiCl, for the ...Scheme 3.14 Application of the alkoxo turbo‐Grignard variant, s‐Bu2Mg·LiOR (...Figure 3.7 Calculated form of the magnesiate transition state formed during ...Figure 3.8 Solid state structure of [i‐PrMgCl(THF)]2[MgCl2(THF)2]2, compound...Scheme 3.15 Synthetic route to the turbo‐Hauser base, TMPMgCl·LiCl.Scheme 3.16 Comparative ability of TMPMgCl·LiCl and i‐Pr2NMgCl·LiCl to effec...Scheme 3.17 Selective magnesiation of diethyl bromoisophthalate with TMPMgCl...Scheme 3.18 Examples of selective deprotonation/magnesiation with the turbo‐...Figure 3.9 Solid state structures of (a) the sodium trialkylcalciate, compou...Scheme 3.19 Synthetic route to heterobimetallic diphenylphenoxides and the s...Scheme 3.20 Enolization of 2,4,6‐trimethylacetophenone by the heterobimetall...Scheme 3.21 Calciate‐catalyzed (5 mol% 55) hydroamination of diphenylbutadiy...Scheme 3.22 The principal mechanistic steps invoked in alkaline earth cataly...Scheme 3.23 Illustrative protonolysis of alkaline earth hexamethyldisilazide...Scheme 3.24 Protic (a) and hydridic (b) alkaline earth catalytic cycles invo...Scheme 3.25 Intermolecular hydroamination catalyzed by alkaline earth anilid...Scheme 3.26 Generic scheme for the alkaline earth‐catalyzed dehydrocoupling ...
4 Chapter 4Figure 4.1 Dimeric, tethered, and di‐nucleating types of heterobimetallic ca...Scheme 4.1 Synthesis of RuZn complexes (2–4). Counter‐ions omitted for clari...Figure 4.2 Computed reaction profile for the formation of 2, 3, and 4. Schem...Scheme 4.2 Synthesis of Ru–In and Ru–Ga complexes (5–8).Figure 4.3 Ru–In adduct intermediate to formation of 5, showing sources of e...Scheme 4.3 Synthesis of Ru–M complexes (9–12) (M = Li, Mg, Zn) and subsequen...Figure 4.4 (a) Molecular structure of 12. Ellipsoids are represented at 30% ...Figure 4.5 Computed energy profile for Zn‐assisted and Zn‐free C–H reductive...Figure 4.6 Electronic structure analysis of 12′ and its Mg cogener 12′...Scheme 4.4 Bimetallic complexes for catalytic hydrogenation of alkynes.Figure 4.7 Selected Wiberg bond index values for the reaction between 13´...Figure 4.8 Selected natural charge values derived from natural population an...Figure 4.9 General structure of bimetallic complexes prepared by Lu et al.Figure 4.10 Selected natural orbitals obtained from a CASSCF calculation of ...Figure 4.11 Possible pathways investigated computationally for the hydrogena...Figure 4.12 Relative free energies of the transition state for and product o...Scheme 4.5 Activation of nitrogen by FeAl− complex, and formal 4‐elect...Figure 4.13 Qualitative diagram showing MO occupation for the [CoM′‐N2] − se...Scheme 4.6 Silylation of nitrogen catalysed by CoCo complex.Figure 4.14 (a) DFT‐calculated mechanism for the CoCo‐mediated silylation of...Figure 4.15 Energy difference between open and closed forms of complex 14 de...Scheme 4.7 Pd–M complexes (M = Al, Ga, In), and catalytic hydrosilylation of...Scheme 4.8 Pd–M complexes (M = Li, Cu, Zn) and catalytic hydrosilylation of ...Figure 4.16 Effect of changing supporting metal on a range of calculated par...Figure 4.17 Simplified mechanism for the coordination insertion polymerizati...Figure 4.18 Selected metallocene‐based heterobimetallic catalysts for olefin...Figure 4.19 Structures of (half)‐metallocene‐based catalysts 19–22.Figure 4.20 Solid‐state molecular structure of 21, obtained by X‐ray diffrac...Figure 4.21 Free energies and DFT‐optimized structures of (η5‐2,5‐Me2C4H2NAl...Figure 4.22 Solid‐state molecular structure of 23, obtained by X‐ray diffrac...Figure 4.23 Proposed mechanism, based on experimental and computational work...Scheme 4.9 Synthesis of the Ti/Zr heterobimetallic catalyst 24.Figure 4.24 Proposed scenario for enhanced polyolefin chain branching mediat...Scheme 4.10 Synthesis of the heterobimetallic catalysts 25–27.Figure 4.25 Branches/1000 C in the polyethylene produced by the mixture of m...Figure 4.26 Energetic profiles (kcal/mol) for propagation (blue) and termina...Figure 4.27 Proposed mechanism for 1‐hexene generation and subsequent copoly...Figure 4.28 Solid‐state molecular structure of 28 obtained by X‐ray diffract...Figure 4.29 Solid‐state molecular structure of 29 obtained by X‐ray diffract...Scheme 4.11 Metalation of mononuclear complex (NON)Ni(C4H7) by ZnBr2, to giv...Figure 4.30 Influence of coordination pattern in the activity of heterobimet...Figure 4.31 X‐ray crystal structure of 31 ([NiNa(Ph)(PPh3)(L3)][BArF 4]). L3...Figure 4.32 Structure–activity correlation plot showing the effect of differ...Figure 4.33 Solid‐state molecular structure of 32 obtained by X‐ray
