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1 Chapter 1Figure 1.1 The general principles demonstrated by (a) a heterobimetallic ate...Scheme 1.1 A generic directed ortho‐deprotometalation strategy incorporating...Scheme 1.2 Representation of a generic directed ortho‐lithiation strategy.Scheme 1.3 Steric effects on the directed ortho‐lithiation of aromatic ester...Figure 1.2 Dimer structures of (a) i‐Pr₂NC(O)‐2‐Et‐C₆H₃Li(THF) 5 and (b) hem...Scheme 1.4 The rearrangement of [2‐(Me₂NCH₂)C₁₀H₆Li‐1]₂(dman) 9 in hot tolue...Scheme 1.5 Selective magnesiation of an alkyl benzoate using magnesium amide...Scheme 1.6 Treatment of methyl 1‐phenylsulfonylindole‐3‐carboxylate with (i‐...Scheme 1.7 Ortho‐magnesiation of a borylbenzene via internal reaction of N‐m...Figure 1.3 Structure of the orthoC,N‐magnesiated dimer of 25(12).Scheme 1.8 The use of (^DipNacnac)MgTMP 27 in pyrazine deprotometalation.Figure 1.4 Molecular structures of (a) [{PhN(H)}₂(t‐BuO)LiNaK(TMEDA)₂]₂31₂ a...Scheme 1.9 Reactivity of metal alkoxides towards toluene in C₅D₅N. L = η⁶ : ...Figure 1.5 Molecular structure of [{4,6‐Me₂C₆H₂(O)(CH₂)}LiNa(TMEDA)]₄34₄....Figure 1.6 Molecular structure of the core of (PhK)₄(PhLi)(t‐BuOLi)(THF)₆(C₆Figure 1.7 Molecular structures of (a) Li₄K₄Np_2.75(t‐BuO)_5.2536 and (b) Li₄KFigure 1.8 Molecular structure of [Li₄KNp₂(Ot‐Bu)₃]₂38₂ (K = dark purple, Li...Scheme 1.10 The elaboration of ferrocene employing 39. Fc = ferrocenyl, n = ...Scheme 1.11 Reactions of TMPMgCl(LiCl) 41 with 5‐bromopyrimidine (top) and a...Scheme 1.12 Ortho‐magnesiation by TMP₂Mg(LiCl)₂44 ^TMP of an aromatic bis(dim...Scheme 1.13 Halogen–zinc exchange in a para‐substituted aromatic iodide.Scheme 1.14 Use of a lithium zincate to avoid intermediate rearrangement of ...Scheme 1.15 The contrasting reactivity of an allyl 2‐iodophenyl ether with M...Scheme 1.16 Investigation of the migratory aptitude of lithium dialkylphenyl...Scheme 1.17 Tert‐butyl as a nontransfer group; 65 incurs the halogen–zinc ex...Scheme 1.18 Treatment of methyl 4‐iodobenzoate with 65 preceded allylation (...Scheme 1.19 Addition reaction involving the transmetalation of putative lith...Figure 1.9 Molecular structures of (a) solvated (DMBA)₃ZnLi 76 and (b) (DMBA...Scheme 1.20 Competing SIP and CIP formation in Me₃ZnLi chemistry.Scheme 1.21 Halogen–metal exchange of p‐iodoanisole with cuprate 81 at −78 °...Scheme 1.22 Reaction of methyl p‐iodobenzoate and 81, with subsequent oxidat...Scheme 1.23 The contrasting reactivity of an epoxide with n‐BuLi and differe...Figure 1.10 Structures of phosphine‐stabilized (a) CIP [Me₂Cu][Cu(PPh₃)] or ...Scheme 1.24 Synthesis of lithium dimethylcuprate 83.Figure 1.11 Structures of phenylcuprate species (a) [Ph₆Cu₃Li₂]⁻ in 98Figure 1.12 Selected higher‐order cuprates (a) Ph₅Cu₂Li₃ (SMe₂)₄101 and (b) ...Figure 1.13 Molecular structures of the dimers of (a) (DMBA)₂CuLi 103 and (b...Figure 1.14 Structures of (a) SIP [{(Me₃Si)₃C}₂Cu][Li(THF)₄] 106, and (b) be...Figure 1.15 Molecular structure of [C₆H₄{CH₂N(Me)CH₂CH₂NMe₂}‐2]₂Cu(Br)Li₂112Figure 1.16 Molecular structures of (a) polymeric (DMBA)₂Cu(CN)Li₂(THF)₄114,...Scheme 1.25 Use of ate complex t‐Bu₃ZnLi 65 as a solid‐phase metalating agen...Scheme 1.26 Synthesis oft‐Bu₂Zn(TMP)Li 1.Scheme 1.27 Application of 1 in biaryl synthesis.Figure 1.17 Proposed intermediates in the metalation of selected heteroaroma...Figure 1.18 A generalized alkali metal zincate.Scheme 1.28 Transmetalation of lithioanisole to variously solvated ortho‐zin...Scheme 1.29 The anionic Fries rearrangement and its avoidance using lithium ...Scheme 1.30 Comparing the performance of Cd and Zn reagents in aromatic halo...Scheme 1.31 Synthesis of i‐Bu₃Al(TMP)Li 144.Scheme 1.32 Ortho‐alumination of a functionalized aromatic ring.Figure 1.19 Model aluminate 149, obtained by sequentially treating ArC(O)Ni‐...Scheme 1.33 i‐Bu₂Al(TMP)₂Li 150 has enabled the conversion of 4‐halo‐a...Figure 1.20 Molecular structures of aluminated precursors 154 and 155 to (a)...Figure 1.21 Representation of the Gilman amidocuprate (TMP)₂CuLi.Scheme 1.34 A generalized view of directed ortho‐cupration.Figure 1.22 Molecular structure of Lipshutz cuprate dimer [(TMP)₂Cu(CN)Li₂(T...Figure 1.23 Molecular structures of organoamidocuprates (a) [MesCu(NBn₂)Li]₂Scheme 1.35 Selective formation of Gilman and Lipshutz‐type cuprates from Cu...Figure 1.24 Molecular structures of (a) Gilman amidocuprate dimer of (TMP)₂C...Figure 1.25 (a) Schematic of an adduct cuprate structure‐type and (b) molecu...Figure 1.26 Molecular structures of heteroleptic cuprates (a) [(TMP)(DMP)Cu(...Figure 1.27 Molecular structures of the dimers of thiocyananto(amido)cuprate...Figure 1.28 Examples of cyanatocuprates (a) [(TMP)₂Cu(OCN)Li₂(THF)]₂172₂ and...Figure 1.29 Isomers of (TMP)₄Cu₂Li₂; (a) dimer of conventional Gilman cuprat...Figure 1.30 Structurally characterized organoamidocuprate aggregates (a) Ph(...Figure 1.31 The dimer of lithium argentate (TMP)₂Ag(CN)Li₂(THF) 179.Scheme 1.36 Examples of directed deprotometalation using lithium argentate 1...Figure 1.32 Molecular structure of the dimer of [2‐(i‐Pr)₂NC(O)‐C₆H₄]₂AgLi(T...Scheme 1.37 Lithium argentate 179 shows good functional group tolerance when...

2 Chapter 2Figure 2.1 Common oligomeric structures adopted by the organolithium reagent...Figure 2.2 Part of the infinite solid‐state ladder structure of PhLi 2.Scheme 2.1 Disruption of the polymerization of MeLi tetramers 1 by common Le...Figure 2.3 Molecular structures of n‐BuLi 7 (left) and t‐BuLi 8 ...Scheme 2.2 Disruption of the n‐BuLi hexamer by polydentate Lewis donor...Scheme 2.3 Deprotonation of PMDETA by coordinated n‐BuLi producing 16....Figure 2.4 Distortion to the central Li₂C₂ rings of dimeric t‐BuLi and...Scheme 2.4 Donor dependence of n‐BuLi reactivity towards benzene and t...Scheme 2.5 Contrasting solvent‐dependent reactivity of BuLi with the heteroc...Figure 2.5 Polymeric structures of trimethylsilylmethylsodium 24 (top) and b...Scheme 2.6 Effect of TMEDA on structures of trimethylsilylmethylsodium and b...Figure 2.6 Common secondary amines employed for metallation chemistry.Scheme 2.7 Simplified bonding in metal‐amide oligomers, using a cyclodimer a...Figure 2.7 Molecular structures of LiDA 35, LiHMDS 36, and LiTMP 37a/37b....Figure 2.8 Representative example of higher‐order and lower‐order structures...Figure 2.9 Influence of the agostic interactions on homo‐, hetero‐ and solva...Figure 2.10 LiCKOR metallation of toluene.Scheme 2.8 Lithiation of sodium 2,4,6‐trimethylphenoxide to yield the hetero...Figure 2.11 Molecular structure of trimetallic alkoxide complex 59 (K = dark...Scheme 2.9 Contrasting reactivity of LiCKOR superbase in the presence and ab...Figure 2.12 Molecular structures of [(THF)₂Li(μ‐Cl)₂Mg(THF)TMP] 60 (left) an...Scheme 2.10 Synthesis of heteroleptic sodium zincate 62 by metallation of be...Scheme 2.11 Contrasting reactivity of a homometallic zinc reagent and a bime...Scheme 2.12 Contrasting reactivity of homoleptic bimetallic HMDS complexes w...Scheme 2.13 Proposed mechanism of addition of diarylmethanes to alkenes cata...Scheme 2.14 Examples of the metallation scope of LiZnt‐Bu₂(TMP).Figure 2.13 Molecular structure of [(THF)Li(TMP)(t‐Bu)Zn(t‐Bu)] Scheme 2.15 Computed transition states for addition versus metallation react...Scheme 2.16 Stoichiometry dependent variable reactivity of LiZn(t‐Bu)₂(TMP) ...Scheme 2.17 Two‐step mechanism of substrate deprotonation with mixed amido/a...Scheme 2.18 Experimental evidence for alkyl dependence upon two‐step mechani...Scheme 2.19 Disproportionation of anisolyl lithium zincate and the molecular...Figure 2.14 Propagation of EtZn(Et)(TMP)Li 75 into a polymer.Scheme 2.20 Synthetic approach and molecular structures of [EtZn{C₁₀H₆C(=O)NFigure 2.15 Molecular structures of [{(C₅H₅)Fe(C₅H₄)}₂Zn(TMEDA)] 79 (left) a...Scheme 2.21 Cascade of reactions upon deprotonating ferrocene with dialkyl‐a...Figure 2.16 Molecular structure of [(TMEDA)Na(TMP)(t‐Bu)Zn(t‐Bu)...Scheme 2.22 Stoichiometry dependent mono‐ and di‐deprotonation of aromatic s...Scheme 2.23 Meta‐deprotonation of N,N‐dimethylaniline using sodium TMP–zinca...Figure 2.17 Molecular 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⁻Al^III(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)][BAr^F 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 diffract...Figure 4.34 Metal‐catalyzed coordination–insertion mechanism for the ROP of ...Figure 4.35 Bifunctional mechanism for the ROP of lactide (A: Lewis acid; B:...Figure 4.36 Concept of a bifunctional mechanism for the ROP of lactide invol...Figure 4.37 Selected structures of ‘M₁–O–M₂’ heterobimetallic catalysts for ...Figure 4.38 Solid‐state molecular structure of 39 obtained by X‐ray diffract...Figure 4.39 Solid‐state molecular structure of 40 obtained by X‐ray diffract...Scheme 4.12 Synthesis of Ti monometallic and Ti/Zn heterobimetallic complexe...Figure 4.40 Solid‐state molecular structure of 41 obtained by X‐ray diffract...Scheme 4.13 Synthesis of Al/Zn heterobimetallic complex 42.Figure 4.41 Solid‐state molecular structure of 43 obtained by X‐ray diffract...Scheme 4.14 Synthesis of Ge/Li and Sn/Li heterobimetallic complexes 44 and 4...Figure 4.42 Structure of Cr/Al complex 46 and heterobimetallic catalysis str...Figure 4.43 Catalytic cycle for the CO₂/epoxide copolymerization, including ...Figure 4.44 Computed potential energy surface of the first propagation cycle...Figure 4.45 Illustration (not to scale) of the potential energy surface for ...Figure 4.46 Chain shuttling mechanism.Figure 4.47 Solid‐state molecular structure of 47 obtained by X‐ray diffract...Scheme 4.15 Synthesis of RE/zinc heterometallic complexes by ligand redistri...Figure 4.48 Solid‐state molecular structure of La/Zn complex 48 obtained by ...Figure 4.49 Solid‐state molecular structure of Co/La complex 49 obtained by ...Scheme 4.16 Synthesis of heterobimetallic Zn/Mg complex 50.Figure 4.50 Heterobimetallic complexes supported by a macrocyclic diphenolat...Figure 4.51 Solid‐state molecular structure of Zn/In complex 51 obtained by ...Figure 4.52 ΔH^‡ (solid squares, with errors ±1.3) and |ΔS‡| (open circ...

5 Chapter 5Figure 5.1 Mononuclear borocations classified on the basis of coordination n...Figure 5.2 Summary of a few common synthetic strategies employed for cationi...Figure 5.3 Popular experimental and computational methods for the determinat...Scheme 5.1 Isodesmic reactions to calculate chloride, fluoride, and hydride ...Scheme 5.2 Two coordinate C‐bonded Mes₂B⁺ borinium cation and its reaction w...Scheme 5.3 Reactivity behaviour of Mes₂B⁺ borinium cation; with H₂ and HSiEtScheme 5.4 Reactivity of [(i‐Pr₂N)₂B][B(C₆F₅)₄] with unsaturated molecules....Scheme 5.5 Adduct formation between borocation 13 and Et₃PO demonstrating th...Figure 5.4 Initial examples of NHC‐stabilized aryl‐ and alkyl‐borenium catio...Scheme 5.6 Synthesis of NHC‐stabilized borenium cations (top) and reactivity...Scheme 5.7 Generation of NHC‐stabilized iminioborenium cation via silylation...Scheme 5.8 Dehydrogenative cationic borylation of NHC‐BH₃ adduct and generat...Figure 5.5 NHC‐ and CAAC‐stabilized dibenzo[b,f]borepinium (n = 2) and 9‐bor...Scheme 5.9 General scheme for the synthesis of air stable π‐conjugated benzo...Figure 5.6 Structure of polycyclic diborenium ion 32[NTf₂]₂ and its solid‐st...Figure 5.7 NHSi–borenium cation and canonical structures of silylene support...Scheme 5.10 Ylide‐stabilized borenium cation.Figure 5.8 Structure of phosphine‐stabilized borenium cation 36, the counter...Scheme 5.11 Phosphine‐stabilized borenium cation and its reactivity with amm...Figure 5.9 Structurally characterized bis(phosphinimino)amide‐stabilized bor...Scheme 5.12 Synthesis of bis(phosphinimino)amide supported borenium cations....Scheme 5.13 A series of borocations stabilized by tunable diazadienes.Figure 5.10 Single‐crystal X‐ray structure of (a) [BrHB(dcpe)]Br, (b) [H₂B(t...Figure 5.11 Examples of boronium cations.Figure 5.12 Bisphosphine‐stabilized boronium cation 52[BF₄] and its phosphon...Scheme 5.14 Amidinato silylene‐stabilized borenium cations.Figure 5.13 Examples of a few selected organoaluminium cations.Scheme 5.15 A few common synthetic methods to generate cationic aluminium sp...Scheme 5.16 Two coordinated organoaluminium and gallium cations.Figure 5.14 Molecular structures of (car)borane‐complexed aluminium cations ...Scheme 5.17 Tetracoordinated aluminium cations and reactivity with Lewis bas...Figure 5.15 Zwitterionic “Meisenheimer type” pentacoordinated aluminium comp...Scheme 5.18 THF adduct of bis(allyl)‐substituted aluminium cations.Scheme 5.19 NHC‐stabilized dimeric aluminium dication 67 and monomeric alumi...Scheme 5.20 Cationic aluminium hydride complexes stabilized by NHC via norma...Scheme 5.21 Selected example of NHC coordinated alkyl aluminium cations.Scheme 5.22 Cationic alkylaluminium complexes stabilized by redox active non...Figure 5.16 Examples of aluminium cations supported by N,N'‐chelating li...Figure 5.17 Molecular structure of organoaluminium cation 86[MeB(C₆F₅)₃]....Scheme 5.23 Synthesis of a π‐electron‐donating ligand‐stabilized cationic al...Figure 5.18 Examples of a few selected miscellaneous aluminium cations.Figure 5.19 A few selected structurally characterized gallium and indium cat...Scheme 5.24 Nitrile adduct of NHC‐stabilized gallium chloride cations.Scheme 5.25 An NHC‐stabilized cationic indium complex.Figure 5.20 [N,N',O]‐coordinated indium cations.Scheme 5.26 Cationic indium complexes supported by salen ligand.Figure 5.21 Structure of the cation in [Ga(PPh₃)₃]⁺[Al{OC(CF₃)₃}₄]⁻·1....Figure 5.22 Examples of indium(I) cations.Figure 5.23 Examples of Tl(I) cations.Scheme 5.27 Generalized scheme for hydroboration reaction with active borane...Figure 5.24 Reaction pathway for hydroboration of alkyne.Scheme 5.28 Hydroboration of pyridines catalyzed by NH₄BPh₄.Figure 5.25 Proposed reaction pathway for regioselective 1,4‐hydroboration o...Scheme 5.29 Hydrosilylation and deoxygenation of ketones catalyzed by 13[B(CScheme 5.30 Hydrosilylation of carbonyl with HSiEt₃ catalyzed by borenium ca...Figure 5.26 Proposed catalytic cycle for hydrosilylation of benzaldehyde cat...Scheme 5.31 Borenium cation mediated activation of H₂ in the presence of ext...Figure 5.27 Proposed hydrogenation pathway for carbene‐stabilized borenium i...Scheme 5.32 Assorted mesoionic carbene‐stabilized borenium cations as cataly...Figure 5.28 Chiral carbenes (112 and 113), borenium cations (115–116),...Figure 5.29 Chiral borane adducts as precursors for borenium catalysts for h...Scheme 5.33 Aluminium cation‐catalyzed hydroboration of carbonyls.Scheme 5.34 Proposed mechanism for cationic aluminium species‐catalyzed hydr...Scheme 5.35 Selective hydroboration of ketones catalyzed by complex 65a.Scheme 5.36 Selective hydroboration of alkynes catalyzed by complex 65a.Scheme 5.37 Pentacoordinated aluminium cation‐catalyzed cyanosilylation of c...Scheme 5.38 Organoaluminium cation‐catalyzed cyanosilylation of carbonyls.Scheme 5.39 Hydrosilylation of carbonyls and imines catalyzed by complex 95[...Scheme 5.40 Hydrosilylation of alkenes and alkynes catalyzed by aluminium hy...Figure 5.30 Plausible mechanisms for the hydrosilylation of alkene catalyzed...Scheme 5.41 Hydrosilylation of ketones catalyzed by a cationic aluminium com...Figure 5.31 Proposed mechanism for the Tischenko reaction catalyzed by an al...Scheme 5.42 Hydroamination of (top) primary and (bottom) secondary amino alk...Figure 5.32 Coordination–insertion mechanism proposed for the ROP of ε‐capro...Scheme 5.43 C–C bond formation through activation of alcohols by cationic ga...Scheme 5.44 Olefin epoxidation catalyzed by cationic gallium and aluminium c...Scheme 5.45 Catalytic transfer hydrogenation of alkenes.Scheme 5.46 Hydroarylation reactions catalyzed by cationic gallium and indiu...Scheme 5.47 Trimolecular hydroarylation of alkynes catalyzed by a Ga(I) comp...Figure 5.33 Cationic gallium‐catalyzed hydroarylation of alkynes followed by...Scheme 5.48 Cycloisomerization of enyne.Scheme 5.49 Tandem carbonyl‐olefin metathesis catalyzed by a cationic galliu...Scheme 5.50 Synthesis of spiro‐ortho esters (SOEs).Scheme 5.51 ROP of epoxide catalyzed by a cationic indium complex.Scheme 5.52 A variety of cationic indium complexes utilized for the ROP of a...Figure 5.34 Cationic indium complexes for polymerization of lactide/ε‐caprol...

6 Chapter 6Figure 6.1 Lithium amide complexes incorporating (−)‐sparteine or (+)‐sparte...Figure 6.2 Lithium enolate 9 and the more complex head‐to‐head aggregated he...Scheme 6.1 Diasteromeric resolution in camphor‐derived spirocycle 11₂′Figure 6.3 Recently studied Evans‐type propionate enolates.Scheme 6.2 Evans enolate 12 ^Bn,Me has demonstrated variable agglomeration be...Figure 6.4 Illustrative solvent‐dependent complexation of amino alkoxide 13 ...Figure 6.5 Recently studied products of Weinreb amide enolization.Scheme 6.3 Solvent replacement in 16₄(THF)₄ through 16₄(Py)₄ at −95 °C with ...Figure 6.6 Selected N,X‐lithium amides and the complex between the amide of ...Figure 6.7 Selected complexes between N,X‐ and related lithium amides and n‐...Figure 6.8 Trinuclear 19 ^TIPS ₂[n‐Bu(t‐Bu)CHOLi].Scheme 6.4 LTMP oligomers 23₄ (left) and 23₃ (right) present in d₆‐benzene a...Figure 6.9 24 ^A–D have been found by a combination of PGSE and DOSY te...Scheme 6.5 Exchange rate constants (s⁻¹) between (2‐Me₂N‐C₆H₄Li)₄25₄, ...Scheme 6.6 35 (Less water) was found to be a THF‐solvated CIP in that solven...Scheme 6.7 (i) Lithium amide‐mediated amidation and transamidation processes...Figure 6.10 Dimeric structures for 2‐MeTHF complexes of 36–38 as established...Scheme 6.8 [PhN=N(C₁₀H₆)O]₆Mg₂Li₂42, based on two truncated cubes sharing a ...Scheme 6.9 The selective dimagnesiation of un‐ and monosubstituted arenes su...Scheme 6.10 Proposed equilibrium in d₁₂‐cyclohexane solution between sodium...Scheme 6.11 (i) Potential solution structures of 50 in THF (solid‐state stru...Scheme 6.12 (i) Solution behaviour of LiCl‐free DAMgCl 57 in THF, and (ii) t...Scheme 6.13 66(THF)₄ has been shown to undergo dismutation in THF to give 67Scheme 6.14 The convoluted equilibrium resulting from the rearrangement of 6...Scheme 6.15 Using lithium amide 23 along with 69 as a TMT agent in the deriv...Figure 6.11 Colour‐coded structure of 72 (left) and selected nOes associated...Scheme 6.16 The effects of order on the addition of the single‐metal compone...Scheme 6.17 Proposal for the reaction of CdCl2 with 23 and a demonstration ...Scheme 6.18 Proposed solution equilibrium between CIP 79₂ and its SIP form 7...Scheme 6.19 Top, reactions in Et₂O at −100 °C of RLi (n = 2 or less, R = Me₃Scheme 6.20 Rapid injection (RI) synthesis of Cu(III) intermediate 92 using ...Scheme 6.21 Synthesis of Cu(III) intermediate 95 using MeCu(¹³CN)Li 96.Figure 6.12 Proposed major (left) and minor (right) π‐complexes achieved by ...Figure 6.13 In 100, Sol = d₁₀‐OEt₂, which gradually changes to d₈‐THF as m...Scheme 6.22 The structural possibilities elucidated for cuprate 102 in hydro...Scheme 6.23 The effect of gradual THF addition to a hydrocarbon solution of Scheme 6.24 Synthesis of 109 and the ⁷Li NMR spectrum obtained upon dissolvi...Figure 6.14 Depending on their relative populations, heating LTMP 23 and CuT...Scheme 6.25 Synthesis of 112–114 via intermediate 116.Scheme 6.26 Dissociative interchange of Li and TMP in 114, mediated by symme...Scheme 6.27 Proposed two‐step mechanism for AMMZn, in this case of anisole, ...Scheme 6.28 The contrasting reactivities of 118 and 119 towards HTMP in d₆ Scheme 6.29 Contrasting outcomes of the AMMZn of fluoromethylbenzene by sodi...Scheme 6.30 Proposed mechanism (from DFT calculations) for the directed meta...Scheme 6.31 Synthesis of heteroleptic, alkoxide‐containing lithium zincates Scheme 6.32 Concentration‐dependent, dynamic equilibrium of 133 with its mon...Scheme 6.33 A temperature‐dependent equilibrium process affecting 135 in THF...

7 Chapter 7Scheme 7.1 Reports of nucleophilic boron compounds prior to boryllithium [Di...Scheme 7.2 Synthesis of boryllithium 4 and its reaction with water.Figure 7.1 Crystal structures of (4·DME)₂ and 4·(THF)₂.Scheme 7.3 Reactivity of boryllithium 4 as a boron nucleophile.Scheme 7.4 (a) Generation of boryl anion 8 as an ate complex of lithium in a...Figure 7.2 Crystal structure of 8.Scheme 7.5 Synthesis and reactivity of 1,2,4,3‐triazaborol‐3‐yllithium 9.Scheme 7.6 Synthesis and reactivity of NHC‐stabilized borole anion 10 (Mes =...Scheme 7.7 Synthesis and reactivity of NHC‐stabilized parent boryl anion 11....Scheme 7.8 Synthesis and reactivity of cAAC‐stabilized parent boryl anion 12Scheme 7.9 Synthesis and reactivity of cyanide‐stabilized λ ³‐tricyanob...Scheme 7.10 Synthesis and reactivity of cAAC‐stabilized dicyanoboryl anion 1...Scheme 7.11 Synthesis and reactivity of NHC‐stabilized dicyanoboryl anion 15Scheme 7.12 Linear dimetalloborylene complex 16 having a nucleophilicity on ...Scheme 7.13 Synthesis and reactivity of borylmagnesium.Scheme 7.14 Generation of borylcopper and borylzinc species from boryllithiu...Scheme 7.15 Generation of borylmagnesium and borylzinc species 9 from 1,2,4,...Scheme 7.16 Generation of borylzinc species from boryllithium 21 and subsequ...Scheme 7.17 Nucleophilic borylation of boron compounds by using boryllithium...Scheme 7.18 Reaction of boryllithium 4 with amino(dibromo)pnictogen [Ar = 2,...Scheme 7.19 Generation of borylmagnesium species by transmetalation of B₂pinScheme 7.20 Reactivity of 41 and 42.Scheme 7.21 Zinc‐catalyzed borylation of aryl halide involving borylzincate Scheme 7.22 Generation of boryl(cyano)cuprate 52 and subsequent reaction wit...Scheme 7.23 Direct carboboration of 1‐phenylpropyne derivatives by using bor...Scheme 7.24 Pd‐catalyzed coupling of borylzinc 58 with bromoarenes and acid ...

8 Chapter 8Figure 8.1 Zinc ate complexes.Scheme 8.1 Halogen–zinc exchange reaction of aryl iodides with Li[ZnMe₃].Scheme 8.2 Enhanced reactivity of di‐anion‐type zincate.Scheme 8.3 Li₂[Znt‐Bu₄]: proton‐proof metalating agent.Scheme 8.4 Negishi‐type cross‐coupling reaction via C–O bond cleavage.Figure 8.2 Heteroleptic zincates: an enormous range of possibilities.Scheme 8.5 Highly regio‐ and chemoselective zincation of (hetero)aromatics....Scheme 8.6 Ortho‐iodination of bromobenzenes without benzyne formation.Scheme 8.7 Chemoselective deprotonative ortho‐alumination with Li[(TMP)Ali‐B...Scheme 8.8 Directed ortho‐cupration with Li₂[(TMP)Cu(CN)Me].Scheme 8.9 Arylcuprate reactivity.Scheme 8.10 Amidocuprate hydroxylation of aromatics.Scheme 8.11 DFT calculations (kcal/mol) to assess the reaction mechanism for...Scheme 8.12 Amidocuprate amination of aromatics.Scheme 8.13 Reduction of carbonyl compounds with M[HZnMe₂].Scheme 8.14 Semi‐reduction of carboxylic acids to aldehydes.Scheme 8.15 Direct conversion of carboxylic acids to ketones by zincates.Scheme 8.16 Silylzincation of alkynes with SiBNOL‐Zn‐ate.Scheme 8.17 Silylzincation of alkynes via Si–B bond activation.Scheme 8.18 Silylzincation of alkenes with SiSiNOL‐Zn‐ate catalyzed by Cp₂Ti...Scheme 8.19 CuCN‐catalyzed silylzincation of alkenes.Figure 8.3 Decomposition of R_F‐organometallics.Scheme 8.20 Zincation of perfluoroalkyl iodide.Scheme 8.21 Perfluoroalkylation and ‐arylation of carbonyl compounds.Scheme 8.22 Aromatic perfluoroalkylation.Figure 8.4 Model DFT calculation on borylzincate formation M06/SVP (Zn) and ...Figure 8.5 Design of a catalytic boration cycle for aryl halides.Scheme 8.23 Substrate scope of aromatic boration.Scheme 8.24 Borylzincation reaction of benzynes.Figure 8.6 Concept for the trans‐selective boration of triple bonds.Scheme 8.25 Fruitless intermolecular diboration of alkynes.Scheme 8.26 Trans‐selective diboration of alkynes.Scheme 8.27 One‐pot diboration reactions.Scheme 8.28 Sequential diboration/Suzuki–Miyaura cross‐coupling, leading to ...Scheme 8.29 Trans‐alkynylboration of alkynes.Scheme 8.30 Transformation of oxaboroles.

9 Chapter 9Scheme 9.1 Synthesis of 1‐aryl‐propenyl copper compounds with N‐coordination...Scheme 9.2 Synthesis of a mixed alkenyl–aryl copper complex.Scheme 9.3 Synthesis of an alkenylcopper–alkyne π‐complex.Scheme 9.4 Syntheses of mononuclear alkenylcopper–carbene complex.Scheme 9.5 Syntheses of dinuclear alkenylcopper–carbene complexes.Scheme 9.6 Revised mechanism of hydroalkylation of alkynes involving a dicop...Scheme 9.7 Syntheses and transformations of butadienyl and octatetraenyl cop...Scheme 9.8 Reaction of butadienyl 1,4‐dicopper tetramer and octatetraenyl tr...Scheme 9.9 Syntheses of styrenyl and butadienyl copper aggregates from zirco...Scheme 9.10 Formation of aromatic dicupra[10]annulenes.Scheme 9.11 Proposed mechanism for the formation of dicupra[10]annulenes.Scheme 9.12 Syntheses of spiro organocopper(I) compounds and organocopper(II...Scheme 9.13 Reductive elimination of tetra‐carbon‐linked copper(III) complex...Scheme 9.14 Synthesis and oxidation of a butadienyl spiro copper complex.Scheme 9.15 Proposed mechanism of the formation of octatetraenyl copper aggr...Scheme 9.16 Syntheses of rigid magnesium organocuprates and organoargentates...Scheme 9.17 Transformation and preliminary reactivity of magnesium organocup...