Chapters authored
Triple Bonds between Bismuth and Group 13 Elements: Theoretical Designs and Characterization
The effect of substitution on the potential energy surfaces of RE13≡BiR (E13 = B, Al, Ga, In, and Tl; R = F, OH, H, CH3, SiH3, Tbt, Ar*, SiMe(SitBu3)2, and SiiPrDis2) is investigated using density functional theories (M06-2X/Def2-TZVP, B3PW91/Def2-TZVP, and B3LYP/LANL2DZ+dp). The theoretical results suggest that all of the triply bonded RE13≡BiR molecules prefer to adopt a bent geometry (i.e., ∠RE13Bi ≈ 180° and ∠E13BiR ≈ 90°), which agrees well with the bonding model (model (B)). It is also demonstrated that the smaller groups, such as R = F, OH, H, CH3, and SiH3, neither kinetically nor thermodynamically stabilize the triply bonded RE13≡BiR compounds, except for the case of H3SiB≡BiSiH3. Nevertheless, the triply bonded RʹE13≡BiRʹ molecules that feature bulkier substituents (Rʹ = Tbt, Ar*, SiMe(SitBu3)2, and SiiPrDis2) are found to have the global minimum on the singlet potential energy surface and are both kinetically and thermodynamically stable. In other words, both the electronic and the steric effects of bulkier substituent groups play an important role in making triply bonded RE13≡BiR (Group 13–Group 15) species synthetically accessible and isolable in a stable form.
Part of the book: Recent Progress in Organometallic Chemistry
The Mechanisms for the Oxidative Addition of Imidazolium Salts to a Group 9 Transition Metal Atom (Co0, Rh0, and Ir0) and a Group 10 Transition Metal Atom (Ni0, Pd0, and Pt0): A Theoretical Study
The potential energy surfaces of the oxidative addition reactions, L2M + imidazoliumcation → product and CpM′L + imidazolium cation → product (M = Ni, Pd, Pt; M′ = Co, Rh, Ir; Cp = η5-C5H5; L = 1,3-aryl-N-heterocyclic carbene (NHC), aryl = 2,4,6-trimethylphenyl), are studied at the M06-L/Def2-SVP level of theory. The theoretical findings show that the singlet-triplet splitting (∆Est = Etriplet − Esinglet) for the L2M and CpM′L species can be used to predict the reactivity for their oxidative additions. That is to say, current theoretical evidence suggests that both a 14-electron L2M complex and a 16-electron CpM′Lcomplex with a better electron-donating ligand L (such as NHC) result in a reduced ∆Est value and facilitate the oxidative addition to the saturated C─H bond. The theoretical results for this study are in good agreement with the obtainable experimental results and allow a number of predictions to be made.
Part of the book: Descriptive Inorganic Chemistry Researches of Metal Compounds
The Effect of Substituent on Molecules That Contain a Triple Bond Between Arsenic and Group 13 Elements: Theoretical Designs and Characterizations
The effect of substitution on the potential energy surfaces of RE13≡AsR (E13 = group 13 elements; R = F, OH, H, CH3, and SiH3) is determined using density functional theory (M06‐2X/Def2‐TZVP, B3PW91/Def2‐TZVP, and B3LYP/LANL2DZ+dp). The computational studies demonstrate that all triply bonded RE13≡AsR species prefer to adopt a bent geometry that is consistent with the valence electron model. The theoretical studies also demonstrate that RE13≡AsR molecules with smaller substituents are kinetically unstable, with respect to the intramolecular rearrangements. However, triply bonded R′E13≡AsR′ species with bulkier substituents (R′ = SiMe(SitBu3)2, SiiPrDis2, and NHC) are found to occupy the lowest minimum on the singlet potential energy surface, and they are both kinetically and thermodynamically stable. That is to say, the electronic and steric effects of bulky substituents play an important role in making molecules that feature an E13≡As triple bond as viable synthetic target.
Part of the book: Chemical Reactions in Inorganic Chemistry