Biomedical subjects
Publications and source records attributed to Didier Bourissou.
The alpha-lactone equivalent lacOCA exhibits remarkable reactivity compared with lactide in nucleophile-catalyzed ROP. PLAs of controlled molecular weights and narrow polydispersities are typically obtained under mild conditions using DMAP and various protic initiators.
In contrast with most of their congeners, acyclic and cyclic C-amino phosphorus ylides behave as genuine carbene and phosphine transfer agents for transition metal centers. They allow the facile synthesis of a variety of metal complexes that feature heteroditopic ligands, such as 1,6-(phosphine)(aminocarbene) systems with a biphenyl backbone.
Monophosphine-boranes were shown to behave as bidentate ambiphilic ligands, whose structural versatility has been illustrated by the preparation of PdII and AuI complexes featuring unusual P --> M-Cl --> B and P --> M --> B interactions, respectively.
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Upon warm up, persistent aminohydrazinocarbenes undergo beta-fragmentation reactions. Experimental as well as computational evidences are reported for the involvement of radical processes. This is the first example of a homolytic fragmentation for a persistent singlet carbene.
Persistent phosphinyl radicals featuring the 2,6-bis(trifluoromethyl)phenyl group were prepared and characterized. Their electronic structure was theoretically investigated, and their low-temperature dimerization into the corresponding diphosphines was found to be strongly inhibited when the sterically very demanding (tert-butyl)(trimethylsilyl)amino substituent was used.
Over the past twenty five years, numerous heteroatom-containing analogues of classical organic moieties have been prepared and structurally characterized. The incorporation of group 13 to 15 heteroelements has often been reported to induce significant geometric distortions compared to the corresponding carbon compounds. These unusual geometries in main group derivatives are examined in this tutorial review, and the precise role of the heteroelements is discussed.
Despite the presence of a single amino substituent, an amino-anthryl-carbene was found to behave as a strong sigma-donor weak pi-acceptor ligand toward rhodium(I) fragments.
Despite through-space and through-bond B-B interactions, the stable 1,3-bora-2,4-diphosphoniocyclobutane-1,3-diyl displays some radical-type behavior, as illustrated by the spontaneous formation of the trans 1,3-adduct with trimethyltin hydride and a B-spiro derivative with bromotrichloromethane.
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Density functional calculations are reported for complexes of general formula [(carbene)RhClL(2)] featuring model phosphino- and aminocarbenes. Both the cis and trans isomers of the rhodium(I) eta(1)-complexes (1-9) were investigated, and the influence of the rhodium co-ligands (L=ethylene, phosphine, or carbon monoxide) was evaluated. In the case of phosphinocarbenes and carbon monoxide as a ligand, a somewhat unusual coordination mode was observed, in which a significant intramolecular Cl-->C(carbene) interaction is present. The propensity of phosphino- and aminocarbenes to behave as four electron donors was also investigated both structurally and energetically on the related eta(2)-complexes 10-18. These results as a whole emphasize the structural versatility of phosphino- compared with aminocarbene complexes.
The concept of through-space versus through-bond interactions on the stabilization of biradical structures with a singlet or triplet ground state is evaluated for the 1,3-diboracyclobutane-1,3-diyls and related congeners. Singlet biradicals are favored when the intermediate units E feature singlet character (PH(2) (+), AsH(2) (+)), while E fragments with triplet character (NH(2) (+)) induce small energy separations between the lowest singlet and triplet states. These considerations are supported by quantum chemical calculations with energy optimization at 1) MCSCF level plus MR-MP2 correction, 2) MR-MP2 level, and 3) two different types of density functional levels for the planar (D(2h)) geometries. The singlet-triplet energy separations in the planar compounds increase with increasing singlet stability of the corresponding E fragments. In addition to this newly developed principal features for singlet stabilization, which primarily occurs in bonded structures with higher main-group elements, the corresponding valence isomers with bicyclobutane, cyclobutene and cis-butadiene structures are investigated.
Catalytic amounts of a protic reagent such as tert-butyl alcohol promote the isomerization of a stable amino-aryl-carbene into a transient azomethine ylide. Deprotonation of an alkyl-aldiminium salt also leads to a transient azomethine ylide, but labeling experiments rule out the transient formation of the corresponding amino-alkyl-carbene. The potential hypersurface between model amino-carbene, aziridine, and azomethine ylide is investigated.
A broad range of (phosphino)(aryl)carbenes, 1b-d, 10a,b, and 14a,b, were prepared by photolysis of their diazo precursors. The influence of the steric and electronic properties of the aryl ring on the structure and stability of these carbenes was studied both experimentally and theoretically. Among the different stabilization modes investigated, those featuring an acceptor as well as a spectator aryl substituent result in stable or at least persistent carbenes that could be completely characterized by classical spectroscopic methods. In marked contrast, the new substitution pattern featuring a donor aryl ring results in a very fleeting carbene.
The first direct complexation of a stable phosphino carbene to a transition metal center is described. Both eta1- and eta2-coordination modes have been characterized spectroscopically. The Fischer-type structure of the eta1-carbene rhodium complex was revealed by an X-ray diffraction study.
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Singlet diradicals are usually not energy minima. As observed by femtosecond spectroscopy, they readily couple to form final sigma bonds. Substituent effects allow lifetimes to increase into the microsecond range. Taking advantage of the properties of hetero-elements, a diradical has been prepared that is indefinitely stable at room temperature. The availability of diradicals that can be handled under standard laboratory conditions will lead to further insight into their chemical and physical properties, raising the likelihood of practical applications, especially in the field of molecular materials such as electrical conductors and ferromagnets.