Compositional disorder in trans-
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Biomedical subjects
Publications and source records attributed to AG Orpen.
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Enhanced reactivity is shown by uncoordinated C identical withC bonds in the proximity of a metal in phosphanylacetylene complexes. cis-[Pt(C(6)F(5))(2)(thf)(2)] reacts with [M(C(6)F(5))(2)(PPh(2)C identical withCPh)(2)] (M=Pt, Pd) to form binuclear complexes containing the novel 2,3-bis(diphenylphosphanyl)-1,3-butadien-1-yl bridging ligand. Substitution of the solvent ligands with, for example, PPh(2)H (see picture) provides species that could be characterized by X-ray crystallography.
Data retrieved from the Cambridge Structural Database for crystal structures containing (µ-diphenylphosphido) metal complexes, [M(2){µ-PPh(2)}] (where M is a d-block element), have been analysed to evaluate the conformational behaviour of these species. The observed distribution of torsion angles about the P-C bonds has been compared with the potential energy surface (PES) for phenyl rotations in a representative species [(AuBr)(2){µ-PPh(2)}](-) computed using the universal force field. Good agreement was obtained between the low-energy (<8 kJ mol(-1) above the global minimum) regions of the PES and the occupied regions of the two-dimensional P-Ph rotor conformation space. Phenyl ring rotations occur by coupled, geared disrotatory and uncoupled conrotatory motions of the phenyl groups in this and other classes of PPh(2) rotors.
Although zeolites and related materials combine nanoporosity with high thermal stability, they are difficult to modify or derivatize in a systematic way. A highly porous metal coordination polymer [Cu3(TMA)2(H2O)3]n (where TMA is benzene-1,3,5-tricarboxylate) was formed in 80 percent yield. It has interconnected [Cu2(O2CR)4] units (where R is an aromatic ring), which create a three-dimensional system of channels with a pore size of 1 nanometer and an accessible porosity of about 40 percent in the solid. Unlike zeolites, the channel linings can be chemically functionalized; for example, the aqua ligands can be replaced by pyridines. Thermal gravimetric analysis and high-temperature single-crystal diffractometry indicate that the framework is stable up to 240 degreesC.