Author
Rinaldo Poli
Other affiliations: University of Burgundy, Universidade Nova de Lisboa, Texas A&M University ...read more
Bio: Rinaldo Poli is an academic researcher from University of Toulouse. The author has contributed to research in topics: Radical polymerization & Polymerization. The author has an hindex of 52, co-authored 483 publications receiving 12096 citations. Previous affiliations of Rinaldo Poli include University of Burgundy & Universidade Nova de Lisboa.
Papers published on a yearly basis
Papers
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TL;DR: Density functional theory performs reasonably well for the difficult problem of predicting the energy splitting between different spin states of transition metal complexes, although careful calibration is needed.
Abstract: Many reactions of transition metal compounds involve a change in spin. These reactions may proceed faster, slower—or at the same rate as—otherwise equivalent processes in which spin is conserved. For example, ligand substitution in [CpMo(Cl)2(PR3)2] is faster than expected, whereas addition of dinitrogen to [Cp*Mo(Cl)(PMe3)2] is slow. Spin-forbidden oxidative addition of ethylene to [Cp*Ir(PMe3)] occurs competitively with ligand association. To explain these observations, we discuss the shape of the different potential energy surfaces (PESs) involved, and the energy of the minimum energy crossing points (MECPs) between them. This computational approach is of great help in understanding the mechanisms of spin-forbidden reactions, provided that accurate calculations can be used to predict the relevant PESs. Density functional theory, especially using gradient-corrected and hybrid functionals, performs reasonably well for the difficult problem of predicting the energy splitting between different spin states of transition metal complexes, although careful calibration is needed.
408 citations
TL;DR: In this paper, the authors summarized the advances in understanding and synthetic scope of CMRP since its discovery and discussed the cobalt-carbon bond formation by dual contribution of reversible termination and degenerative chain transfer, as well as the impact of additives able to coordinate the metal.
323 citations
TL;DR: Iridium-based asymmetric reduction of ketones to chiral enantiomerically enriched alcohols has recently attracted attention by a number of research groups and interest in this area is growing.
300 citations
TL;DR: In coordination chemistry, many reactions involve several electronic states, in particular states of different spin this article, and this phenomenon of multiple-state reactivity has been recognized for some time, both for gas-phase reactions of bare metal ions, and for transition metal complexes in solution.
291 citations
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TL;DR: The new local density functional, called M06-L, is designed to capture the main dependence of the exchange-correlation energy on local spin density, spin density gradient, and spin kinetic energy density, and it is parametrized to satisfy the uniform-electron-gas limit.
Abstract: We present a new local density functional, called M06-L, for main-group and transition element thermochemistry, thermochemical kinetics, and noncovalent interactions. The functional is designed to capture the main dependence of the exchange-correlation energy on local spin density, spin density gradient, and spin kinetic energy density, and it is parametrized to satisfy the uniform-electron-gas limit and to have good performance for both main-group chemistry and transition metal chemistry. The M06-L functional and 14 other functionals have been comparatively assessed against 22 energetic databases. Among the tested functionals, which include the popular B3LYP, BLYP, and BP86 functionals as well as our previous M05 functional, the M06-L functional gives the best overall performance for a combination of main-group thermochemistry, thermochemical kinetics, and organometallic, inorganometallic, biological, and noncovalent interactions. It also does very well for predicting geometries and vibrational frequencies. Because of the computational advantages of local functionals, the present functional should be very useful for many applications in chemistry, especially for simulations on moderate-sized and large systems and when long time scales must be addressed. © 2006 American Institute of Physics. DOI: 10.1063/1.2370993
4,154 citations
TL;DR: 1. Advantages and disadvantages of Chemical Redox Agents, 2. Reversible vs Irreversible ET Reagents, 3. Categorization of Reagent Strength.
Abstract: 1. Advantages of Chemical Redox Agents 878 2. Disadvantages of Chemical Redox Agents 879 C. Potentials in Nonaqueous Solvents 879 D. Reversible vs Irreversible ET Reagents 879 E. Categorization of Reagent Strength 881 II. Oxidants 881 A. Inorganic 881 1. Metal and Metal Complex Oxidants 881 2. Main Group Oxidants 887 B. Organic 891 1. Radical Cations 891 2. Carbocations 893 3. Cyanocarbons and Related Electron-Rich Compounds 894
3,432 citations
TL;DR: In this article, a review of recent mechanistic developments in the field of controlled/living radical polymerization (CRP) is presented, with particular emphasis on structure-reactivity correlations and "rules" for catalyst selection in ATRP, for chain transfer agent selection in reversible addition-fragmentation chain transfer (RAFT) polymerization, and for the selection of an appropriate mediating agent in stable free radical polymerisation (SFRP), including organic and transition metal persistent radicals.
2,869 citations
2,594 citations