On the P‐Coordinating Limit of NHC–Phosphenium Cations toward RhI Centers

Two types of imidazoliophosphane with additional electron‐withdrawing substituents, such as alkoxy or imidazolio groups, are experimentally described and theoretically studied. Diethyl N,N′‐2,4,6‐methyl(phenyl)imidazoliophosphonite is shown to retain a P‐coordinating ability toward a {RhCl(cod)} (cod=cycloocta‐1,5‐diene) center, thus competing with the cleavage of the labile C? P bond. Derivatives of N,N′‐phenylene‐bridged diimidazolylphenylphosphane were isolated in good yield. Whereas the dicationic phosphane proved to be inert in the presence of [{RhCl(cod)}₂], the monocationic counterpart was shown to retain the P‐coordinating ability toward a {RhCl(cod)} center, thus competing with the N‐coordinating ability of the nonmethylated imidazolyl substituent. The ethyl phosphinite version of the dication, thus possessing an extremely electron‐poor P^III center, was also characterized. According to the difference between the calculated homolytic and heterolytic dissociation energies, the N₂C???P bond of imidazoliophosphanes with aryl, amino, or alkoxy substituents on the P atom is shown to be of dative nature. The P‐coordinating properties of imidazoliophosphanes with various combinations of phenyl or ethoxy substituents on the P atom and those of six diimidazolophosphane derivatives with zero, one, or two methylium substituents on the N atom, were analyzed by comparison of the corresponding HOMOs and LUMOs and by calculation of the IR C?O stretching frequencies of their [RhCl(CO)₂] complexes. Comparison of the ν_CO values allows the family of the electron‐poor Im⁺PRR′ (Im=imidazolyl) potential ligands to be ranked in the following order versus (R,R′): P(OEt)₃<(Ph,Ph)<(Ph,OEt)<(OEt,OEt)<PF₃<(Ph,Im)<(Ph,Im⁺)<(OEt,Im⁺). The (Ph,Im) representative is therefore the least electron‐donating phosphane for which coordinating behavior toward a Rh^I center has been experimentally evidenced to date. Ultimate applications in catalysis could be envisaged.     

On the P-coordinating limit of NHC-phosphenium cations toward Rh(I) centers

Two types of imidazoliophosphane with additional electron-withdrawing substituents, such as alkoxy or imidazolio groups, are experimentally described and theoretically studied. Diethyl N,N'-2,4,6-methyl(phenyl)imidazoliophosphonite is shown to retain a P-coordinating ability toward a {RhCl(cod)} (cod = cycloocta-1,5-diene) center, thus competing with the cleavage of the labile C-P bond. Derivatives of N,N'-phenylene-bridged diimidazolylphenylphosphane were isolated in good yield. Whereas the dicationic phosphane proved to be inert in the presence of [{RhCl(cod)}(2)], the monocationic counterpart was shown to retain the P-coordinating ability toward a {RhCl(cod)} center, thus competing with the N-coordinating ability of the nonmethylated imidazolyl substituent. The ethyl phosphinite version of the dication, thus possessing an extremely electron-poor P(III) center, was also characterized. According to the difference between the calculated homolytic and heterolytic dissociation energies, the N(2)C???P bond of imidazoliophosphanes with aryl, amino, or alkoxy substituents on the P atom is shown to be of dative nature. The P-coordinating properties of imidazoliophosphanes with various combinations of phenyl or ethoxy substituents on the P atom and those of six diimidazolophosphane derivatives with zero, one, or two methylium substituents on the N atom, were analyzed by comparison of the corresponding HOMOs and LUMOs and by calculation of the IR C=O stretching frequencies of their [RhCl(CO)(2)] complexes. Comparison of the ν(CO) values allows the family of the electron-poor Im(+) PRR' (Im = imidazolyl) potential ligands to be ranked in the following order versus (R,R'): P(OEt)(3)<(Ph,Ph)<(Ph,OEt)<(OEt,OEt)相似文献   

Entropy in dissimilarity and chirality measures

Within the prospect of quantifying the geometrical dissimilarity of molecular models on the basis of a thermodynamical formalism, the algebra of stereogenic pairing equilibria is reviewed and applied to molecular geometry: developing Rassat's proposition, an interaction energy of two figures F and F is taken as proportional tod _H ^Emphasis>/2 (F, F), whered _H denotes the Hausdorff distance. IfG is a group of rotations in E _n the geometrical version of the general equation (E) of the chemical algebra defines a distance extensionD _p(F,F) ofd _H(F,F), which is independent of the orientations of F and F, and where the coefficientp is interpreted as the reciprocal of a temperature-like parameter:p 1/T. At K (p = ), no formal entropy contributes to the definition of the uniform distanceD . At K (p = 0), the discrimination between homo- and hetero-pairing of figures by the harmonic distance Do is averaged over orientation states. Temperature-dependent chirality measuresc _p are derived fromD _p, andc is analogous to Mislow's chirality measure. If T and oT are normalized enantiomorphic triangles with coincident centroids inE ₂,c _p(T) =D _p (T, T) is calculated forp = 0 andp = , and discussed for 0 <p < . Finally, the Hausdorff interaction model is putatively related to energy profiles versus dihedral angle inmeso- anddl-molecules.     

Layer-by-layer assembled composite films of side-functionalized poly(3-hexylthiophene) and CdSe nanocrystals: electrochemical, spectroelectrochemical and photovoltaic properties

Regioregular poly(3-hexylthiophene) containing one diaminopyrimidine side group per ten repeat units (P3HT-co-P3(ODAP)HT) can form molecular composites with 1-(6-mercaptohexyl)thymine capped CdSe nanocrystals (CdSe(MHT)) via hydrogen bonds directed molecular recognition. Here we report complementary spectroscopic, electrochemical and spectroelectrochemical investigations of both the functionalized poly(thiophene) and its composite with the nanocrystals, the latter being fabricated using the layer-by-layer (LbL) deposition technique. UV-Vis-NIR and Raman spectroelectrochemical investigations unequivocally show that the onset of the first anodic peak in the cyclic voltammogram of the copolymer can be attributed to the oxidation of the pi-conjugated backbone in the polymer chains. For this reason, it is possible to determine the width and the position of its band gap (corresponding to the pi-pi* transition) by UV-Vis spectroscopy combined with cyclic voltammetry. These studies show that the polymer exhibits a slightly larger band gap with the HOMO level insignificantly lower in energy (by 0.03 eV) as compared to the case of regioregular poly(3-hexylthiophene) of comparable degree of polymerization. Hydrogen bond interactions of the polymer with CdSe(MHT) in the molecular composite result in a hypsochromic shift of the band corresponding to the pi-pi* transition from 504 nm to 488 nm. This can be taken as a spectroscopic manifestation of the conformational changes induced by shortening of the conjugation length. The observed spectral modifications are consistent with electrochemically determined lowering of the polymer HOMO level (from -4.91 eV in the pure polymer to -4.99 eV in the composite). Cyclic voltammetry studies supported by spectroelectrochemistry also show that the redox stability of CdSe(MHT) in the molecular composite with P3HT-co-P3(ODAP)HT is lower than that determined for stearate-capped nanocrystals. Their irreversible oxidation starts at E = +0.7 V vs. Ag/0.1 M Ag(+)i.e. at potentials by ca. 0.3 V lower than the oxidation of stearate stabilized CdSe nanocrystals of the same size. We show that-despite these modifications-the alignment of the HOMO and LUMO levels of the composite components remains appropriate for its use in hybrid solar cells, which is demonstrated by the photovoltaic effect observed for the LbL-processed composite sandwiched between two electrodes.     

Carbo-mer of Barrelene: A Rigid 3D-Carbon-Expanded Molecular Barrel

After extensive studies of 1D and 2D skeletal carbo-mers based on C₈ π-conjugating dialkynylbutatriene units (DABs: ∼C≡C−(R)C=C=C=C(R)−C≡C∼) bridging sp or sp² centers in carbo-butene, carbo-xylylene or carbo-benzene derivatives, 3D versions are envisaged through carbo-barrelenes and partially reduced derivatives thereof where two or three DAB blades span a bridge between sp³ carbinol vertices or ether thereof. For R=Ph, stable representatives were synthesized through a pivotal [6]pericyclynedione, and extensively characterized by spectroscopic, electrochemical and crystallographic methods. Density functional theory calculations allow detailed analysis of structural and electronic features of the 7 Å high C₂₆ barrel-shaped molecules, and show that they can behave as cages for ionic species. Beyond aesthetical concerns, the results could open prospects of applications in host-guest supramolecular chemistry and single molecule charge transport.     

Demonstration of Green Solvent Performance on O,S,N-Heterocycles Synthesis: Metal-Free Click Chemistry and Buchwald—Hartwig Coupling

The development of new and greener approaches to organic synthesis has been a trend in recent years. Continuing the latest publications of our team, in this work, we demonstrate the efficiency of three solvents: eucalyptol (1,8-cineole), cyclopentyl methyl ether (CPME), and 2-methyltetrahydrofuran (2-MeTHF) for the synthesis of O,S,N-heterocyclic compounds.     

Phosphine-phosphonium ylides as ligands in palladium-catalysed C2-H arylation of benzoxazoles

As balanced electron-rich P,C-chelating ligands, phosphine-phosphonium-ylides are considered for their ability to in situ promote palladium-catalysed direct C(sp²)-H arylation. Using methyl phosphonium salts of 2,2'-bis(diphenylphosphino)-1,1'-binaphtyl ("methyl-BINAPIUM") as ylide precursors under optimized reaction conditions, arylation of benzoxazole was found to proceed in moderate to high yield to give functional 2-aryl benzoxazoles. A strong anion effect of the non-salt free ylide was evidenced (TfO^- > I^- > PF₆^- ≈ salt-free). This first example of phosphonium ylides as ligands in catalytic C-H activation extends the prospect of their general implementation in homogeneous transition metal catalysis.     

1,4-Dialkynylbutatrienes: synthesis, stability, and perspectives in the chemistry of carbo-benzenes

The π-electron-rich C(8)-conjugated sequence of 1,4-dialkynylbutatrienes is identified as a fragile and fascinating motif occurring in carbo-benzene derivatives, and in Diederich's 1,4-bis(arylethynyl)- or 1,4-bis(triisopropylsilylethynyl)butatriene "capped" representatives, in particular, in tetraalkynylbutatriene. The family of symmetrical 1,4-dialkynylbutatrienes (E-C≡C)RC=C=C=CR(C≡C-E) is extended to functional caps (E=H, CH(3), C≡CPh, CPh=CHBr, or CPh=CBr(2)) with non-alkynyl substituents at the sp(2) vertices (R=Ph or CF(3)). The targets were selected for their potential in appealing retrosynthetic routes to carbo-benzenes, in which the aromatic C(18) macrocycle would be directly generated by sequential metathesis or reductive coupling processes. The functional 1,4-dialkynylbutrienes were synthesized by either classical methods used for the preparation of generic butatrienes (R'Li/CuX-mediated reductive coupling of gem-dihaloenynes or SnCl(2)/HCl-mediated reduction of 3,6-dioxy-octa-1,4,7-triyne precursors). Their spectroscopic and electrochemical properties are compared and analyzed on the basis of the relative extent of total conjugation.