Bent Phosphaallenes With “Hidden” Lone Pairs as Ligands

Phosphaheteroallenes R−P=C=L, with L = N-heterocyclic carbenes (NHCs), can be viewed to a certain extent as phosphaisonitriles stabilized with NHCs, R−P=C:←L. The suitability of these molecules as ligands for coinage-metal ions was investigated and coordination through the central carbon center was observed in most cases. A combination of experiments, spectroscopic methods, and DFT calculations indicates the presence of a hidden electron pair at the carbon center of R−P=C:←L. Remarkably, this lone pair also inserts intramolecularly in C−H bonds showing the carbene-type reactivity which is expected for phosphaisonitriles.     

Impact of C=C/B−N Replacement on the Diels–Alder Reactivity of Curved Polycyclic Aromatic Hydrocarbons

The influence of the replacement of C=C bonds by isoelectronic B−N moieties on the reactivity of π-curved polycyclic aromatic hydrocarbons has been computationally explored by means of density functional theory calculations. To this end, we selected the Diels–Alder cycloaddition reactions of the parent corannulene and its BN-doped counterparts with either cyclopentadiene or maleic anhydride. In addition, the analogous reactions involving larger buckybowls, such as BN-hemifullerene, BN-circumtrindene, and BN-fullerene, have been also considered. It has been found that whereas corannulene behaves as a dienophile, its BN counterpart better acts as a diene. In contrast, the larger BN-curved systems cannot be used as dienes in Diels–Alder reactions, but undergo facile (i.e., low barrier) cycloaddition reactions with cyclopentadiene. The observed trends in reactivity, which cannot be directly explained by using typical frontier molecular orbital arguments, are quantitatively described in detail by means of state-of-the-art computational methods, namely the activation strain model of reactivity combined with the energy decomposition analysis method. The results of our calculations highlight the crucial role of the curvature of the system on the reactivity and its influence on the strength of the orbital interactions between the deformed reactants during their transformations.     

A Germylene Supported by Two 2-Pyrrolylphosphane Groups as Precursor to PGeP Pincer Square-Planar Group 10 Metal(II) and T-Shaped Gold(I) Complexes

An efficient synthesis of 2-di-tert-butylphosphanylmethylpyrrole (HpyrmPtBu₂), by treating 2-dimethylaminomethylpyrrole (HpyrmNMe₂) with tBu₂PH at 135 °C in the absence of any solvent, has allowed the preparation of the new PGeP germylene Ge(pyrmPtBu₂)₂ ( 1 ), by treating [GeCl₂(dioxane)] with LipyrmPtBu₂, in which the Ge atom is stabilized by intramolecular interactions with one (solid state) or both (solution) of its phosphane groups. Reactions of germylene 1 with Group 10 metal dichlorido complexes containing easily displaceable ligands have led to [MCl{κ³P,Ge,P-GeCl(pyrmPtBu₂)₂}] [M=Ni ( 2 ), Pd ( 3 ), Pt ( 4 )], which have an unflawed square-planar metal environment. Treatment of germylene 1 with [AuCl(tht)] (tht=tetrahydrothiophene) rendered [Au{κ³P,Ge,P-GeCl(pyrmPtBu₂)₂}] ( 5 ), which is a rare case of a T-shaped gold(I) complex. The hydrolysis of 5 gave the linear gold(I) derivative [Au(κP-HpyrmPtBu₂)₂]Cl ( 6 ). Complexes 2 – 5 contain a PGeP pincer chloridogermyl ligand that arises from the insertion of the Ge atom of germylene 1 into a M−Cl bond of the corresponding metal reagent. The bonding in these molecules has been studied by DFT/NBO/QTAIM calculations. These results demonstrate that the great flexibility of germylene 1 makes it a better precursor to PGeP pincer complexes than the previously known germylenes of this type.     

Quantitative optical imaging of the pharmacokinetics of fluorescent-specific antibodies to tumor markers through tissuelike turbid media

Fluorescent optical imaging of tumors deep within tissue depends on specific binding of antibodies to the tumors' surface markers. These fluorescent antibodies propagating in the vicinity of the tumor can be attached to and (or) diffused away from it. We illustrate application of a new tool, based on the random-walk theory in turbid media, for extracting the pharmacokinetics of these fluorescent antibodies by data deconvolution, excluding the effect of upper turbid tissue layers.     

Multi-iron wells-Dawson heteropolytungstates. Electrochemical probing of siderophoric behavior in sandwich-type complexes

The demetalation process of 10 multi-iron Wells-Dawson polyoxometalates is studied by cyclic voltammetry and controlled potential coulometry. Eight sandwich-type complexes (alphaalphaalphaalpha-Na(16)[(NaOH(2))(2)(Fe(III))(2)(X(2)W(15)O(56))(2)], alphaalphabetaalpha-Na(14)[(NaOH(2))(Fe(III)OH(2))(Fe(III))(2)(X(2)W(15)O(56))(2)], alphabetabetaalpha-Na(12)[(Fe(III)OH(2))(2)(Fe(III))(2)(X(2)W(15)O(56))(2)], and alphabetabetaalpha-Na(14)[(Mn(II)OH(2))(2)(Fe(III))(2)(X(2)W(15)O(56))(2)] (where X = P(V) or As(V))) and two monomeric complexes (alpha-Na(11)[(P(2)(Fe(III)Cl)(2)(Fe(III)OH(2))W(15)O(59))] and alpha-Na(11)[(As(2)(Fe(III)Cl)(2)Fe(III)OH(2))W(15)O(59))]) were selected for this study. All 10 complexes show Fe(III) waves which are well-separated from the redox activity of the W(VI) centers. At room temperature and under mild conditions, iron release from the complexes is observed upon reduction of the Fe(III) centers. This release is controlled by the ionic strength of the medium, the nature and concentration of the anions present in the supporting electrolyte, and by the pH of the solution. This behavior parallels those described for most siderophores which depend on the same parameters.     

The complex of a bivalent derivative of galanthamine with torpedo acetylcholinesterase displays drastic deformation of the active-site gorge: implications for structure-based drug design

Bifunctional derivatives of the alkaloid galanthamine, designed to interact with both the active site of the enzyme acetylcholinesterase (AChE) and its peripheral cation binding site, have been assayed with Torpedo californica AChE (TcAChE), and the three-dimensional structures of their complexes with the enzyme have been solved by X-ray crystallography. Differences were noted between the IC(50) values obtained for TcAChE and those for Electrophorus electricus AChE. These differences are ascribed to sequence differences in one or two residues lining the active-site gorge of the enzyme. The binding of one of the inhibitors disrupts the native conformation of one wall of the gorge, formed by the loop Trp279-Phe290. It is proposed that flexibility of this loop may permit the binding of inhibitors such as galanthamine, which are too bulky to penetrate the narrow neck of the gorge formed by Tyr121 and Phe330 as seen in the crystal structure.