Computational Methods in Organometallic Catalysis. Yu Lan

profiles for a Pd‐catalyzed conversion of aryl i...Scheme 5.9 Mechanism of Pd‐catalyzed silyation of unsaturated bonds.Figure 5.21 The energy profiles for a model reaction of Pd‐catalyzed bis‐sil...Figure 5.22 The free‐energy profiles for Pd‐catalyzed bis‐silylation of carb...Figure 5.23 The free‐energy profiles for Pd‐catalyzed intermolecular σ‐bond ...Scheme 5.10 Pd‐catalyzed C—H activation of methane.Figure 5.24 The free‐energy profiles for Pd‐catalyzed C—H activation of meth...Scheme 5.11 The transition states of Pd‐mediated C—H bond cleavage of proban...Scheme 5.12 Pd‐catalyzed C—H activation/arylation.Scheme 5.13 The calculated activation free energies for the Pd‐mediated C—H ...Scheme 5.14 Distortion–interaction analysis of the C—H bond cleavage step in...Figure 5.25 The free‐energy profiles for Pd‐catalyzed oxidative coupling of ...Figure 5.26 The free‐energy profiles for Pd‐catalyzed cross‐coupling of alde...Figure 5.27 The zero‐point energy profiles for the first‐reported Pd‐mediate...Scheme 5.15 The key transition states with (5‐231ts and 5‐232ts)...Scheme 5.16 Pd‐mediated covalent chelation‐assisted ortho‐ C(aryl)—H activat...Figure 5.28 The free‐energy profiles for Pd‐catalyzed oxidative coupling of ...Figure 5.29 The free‐energy profiles for the key step of Pd/Cu co‐catalyzed ...Scheme 5.17 The key transition states for the Pd‐mediated CMD‐type meta‐C—H ...Scheme 5.18 The key transition states for the Pd‐mediated CMD‐type meta‐C—H ...Scheme 5.19 The key transition states for the Pd‐mediated CMD‐type selective...Scheme 5.20 The key transition states for the Pd‐mediated CMD‐type covalent ...Figure 5.30 The free‐energy profiles of Pd‐catalyzed intramolecular cross‐co...Figure 5.31 The free‐energy profiles of Pd‐catalyzed β‐arylation of amides. ...Figure 5.32 The free‐energy profiles of norbornene‐assisted Pd‐catalyzed ind...Figure 5.33 The free‐energy profiles of the electrophilic deprotonation via ...Figure 5.34 The free‐energy profiles of Pd‐catalyzed azoles arylation reacti...Figure 5.35 The free‐energy profiles of Pd‐catalyzed intramolecular cross‐co...Figure 5.36 The free‐energy profiles of Pd‐catalyzed intramolecular carbene ...Figure 5.37 The free‐energy profiles of Pd‐catalyzed deformylation through a...Scheme 5.21 General mechanism of Pd‐catalyzed unsaturated bond activations: ...Figure 5.38 The free‐energy profiles for a model reaction of Pd‐catalyzed hy...Figure 5.39 The free‐energy profiles for a Pd‐catalyzed hydroarylation of ol...Figure 5.40 The energy profiles for a model reaction of Pd‐catalyzed hydroge...Figure 5.41 The free‐energy profiles for a model reaction of Pd‐catalyzed hy...Figure 5.42 The free‐energy profiles for Pd‐catalyzed Pauson–Khand reaction....Figure 5.43 The free‐energy profiles for Pd‐catalyzed hydroarylation of imin...Figure 5.44 The zero‐point energy profiles for Pd‐catalyzed alkoxycarbonylat...Figure 5.45 The zero‐point energy profiles for Pd‐catalyzed aminocarbonylati...Figure 5.46 The free‐energy profiles for Pd‐catalyzed tandem azide‐isocyanid...Figure 5.47 The free‐energy profiles for a model reaction of Pd‐catalyzed ca...Figure 5.48 The free‐energy profiles for a model reaction of a redox‐neutral...Figure 5.49 The free‐energy profiles for a model reaction of a redox‐involve...Scheme 5.22 The generation of allylic palladium. (a) Oxidative addition, (b)...Scheme 5.23 A typical mechanism of Pd‐mediated allylic substitution.Figure 5.50 The free‐energy profiles for Pd‐catalyzed Stille coupling with b...Figure 5.51 The free‐energy profiles for Pd‐catalyzed amination of allylic a...Figure 5.52 The free‐energy profiles for Pd‐catalyzed hydroamination of alle...Figure 5.53 The free‐energy profiles for Pd‐catalyzed isomerization of allyl...Figure 5.54 The free‐energy profiles for Pd‐catalyzed carbocyclization of bi...

      6 Chapter 6Scheme 6.1 The possible mechanisms of Pt‐mediated C—H activations.Figure 6.1 Free‐energy profiles for the Pt‐catalyzed oxidation of methane in...Figure 6.2 Free‐energy profiles for the PtI₄‐catalyzed intramolecular C—H an...Scheme 6.2 Possible mechanisms of Pt‐mediated C—H bond cleavage.Figure 6.3 Free‐energy profiles for the PtBr₂‐catalyzed isomerization of eth...Figure 6.4 Free‐energy profiles for the PtCl₂‐catalyzed cyclization of ortho Figure 6.5 Free‐energy profiles for the PtCl₂‐catalyzed isomerization of 1,6...Figure 6.6 Free‐energy profiles for the PtCl₂‐catalyzed cyclization of o‐alk...Figure 6.7 Free‐energy profiles for the PtCl₂‐catalyzed isomerization of oxi...Figure 6.8 Free‐energy profiles for the PtCl₂‐catalyzed cyclopropanation of ...Figure 6.9 Free‐energy profiles for the PtI₂‐catalyzed cycloisomerization of...Scheme 6.3 Pt‐mediated annulation of enynes through a key step of oxidative ...Figure 6.10 Free‐energy profiles for the PtCl₂‐catalyzed Alder‐ene type cycl...Scheme 6.4 The general mechanism of Pt‐mediated alkene functionalizations.Figure 6.11 Free‐energy profiles for the K₂PtCl₄‐NaBr‐catalyzed hydroaminati...Scheme 6.5 PtBr₂‐catalyzed hydroamination of olefins.Figure 6.12 Free‐energy profiles for an amino‐Pt(II)‐catalyzed hydroaminatio...Figure 6.13 Free‐energy profiles for an amino‐Pt(II)‐catalyzed hydroformylat...Figure 6.14 Free‐energy profiles for an amino‐Pt(II)‐catalyzed isomerization...

      7 Chapter 7Scheme 7.1 Possible models of cobalt‐mediated C—H activation.Scheme 7.2 (a) Co‐catalyzed C—H alkylations through olefin insertion and the...Figure 7.1 Free‐energy profiles for the low‐valent Co(0)‐catalyzed arene C—H...Figure 7.2 Free‐energy profiles for the high‐valent Co(III)‐catalyzed arene ...Figure 7.3 Free‐energy profiles for the Co(III)‐catalyzed hydroarylation of ...Figure 7.4 Free‐energy profiles for the Co(III)‐catalyzed hydroarylation of ...Figure 7.5 Free‐energy profiles for the Co(III)‐catalyzed hydroarylation of ...Figure 7.6 Free‐energy profiles for the Co(III)‐catalyzed oxidative alkoxyla...Scheme 7.3 General mechanism of Co‐catalyzed cycloadditions.Figure 7.7 Free‐energy profiles for a model Pauson–Khand reaction. The energ...Figure 7.8 Free‐energy profiles for a Co₂(CO)₈‐catalyzed intramolecular [4+2...Figure 7.9 Free‐energy profiles for a model reaction of CpCo(I)‐catalyzed [2...Figure 7.10 Free‐energy profiles for CpCo(I)‐mediated [2+2] cycloaddition of...Scheme 7.4 The general mechanism of Co‐catalyzed hydrogenation reactions.Figure 7.11 Free‐energy profiles for Co‐catalyzed hydrogenation of carbon di...Figure 7.12 Free‐energy profiles for Co‐catalyzed hydrogenation of carbon di...Figure 7.13 Free‐energy profiles for Co‐catalyzed hydrogenation of alkene th...Figure 7.14 Free‐energy profiles for Co‐catalyzed hydrogenation of alkene th...Figure 7.15 Free‐energy profiles for Co(−I)‐catalyzed hydrogenation of alken...Figure 7.16 Free‐energy profiles for Co‐catalyzed hydrogenation of alkyne. T...Scheme 7.5 Co‐catalyzed direct (a) and transfer (b) hydroformylations.Figure 7.17 Free‐energy profiles for a model reaction of Co‐catalyzed hydrof...Figure 7.18 Free‐energy profiles for a model reaction of Co‐catalyzed transf...Scheme 7.6 Mechanism of transition metal‐mediated diazo transformation.Figure 7.19 Free‐energy profiles for the Cp*Co(III)‐catalyzed annulation of ...Figure 7.20 Free‐energy profiles for the key step of Co‐mediated carboxylati...Scheme 7.7 The resonance structures of Co–nitrene complex (a); Calculated sp...Figure 7.21 Free‐energy profiles for the Co‐catalyzed aziridination of olefi...Figure 7.22 Free‐energy profiles for the Co‐catalyzed amination of isonitril...Figure 7.23 Relative enthalpy profiles for the Co‐mediated nitrene insertion...

      8 Chapter 8Scheme 8.1 General mechanism of Rh‐catalyzed C—H activation and functionaliz...Figure 8.1 Free‐energy profiles for Rh(I)‐catalyzed C2‐selective C—H bond ac...Figure 8.2 Free‐energy profiles for Rh(III)‐catalyzed oxidative C—H/C—H cros...Figure 8.3 Free‐energy profiles for Rh(III)‐catalyzed bipyridine C—H alkylat...Figure 8.4 Free‐energy profiles for the key step of Rh/7‐azaindoline co‐cata...Figure 8.5 Free‐energy profiles for Cp*Rh(III)‐catalyzed C—H bond alkylation...Figure 8.6 Free‐energy profiles for Rh(III)‐catalyzed oxidative Heck‐type co...Figure 8.7 Free‐energy profiles for Rh(III)‐catalyzed alkenylation of 8‐meth...Figure 8.8 Free‐energy profiles for Rh(III)‐catalyzed intermolecular C—H bon...Figure 8.9 Free‐energy profiles for Rh(III)‐catalyzed ortho‐C—H bond activat...Scheme 8.2 The general pathways for the Rh mediated C—C bond cleavage.Figure 8.10 Free‐energy profiles for Rh‐catalyzed intramolecular ring expans...Figure 8.11 Free‐energy profiles for Rh‐catalyzed borylation