A unique family of polyelectrolytes with four different stoichiometric Fe/Ru ratios were prepared and characterized. Pyrolysis in a reducing atmosphere led to crystalline, mixed phase nanomaterials containing iron, ruthenium, and phosphorus with compositions influenced by the structure of the parent polyelectrolytes.
The synthesis and characterization of a series of Group 6 metal pentacarbonyl complexes of air stable primary, secondary, and tertiary phosphines containing ferrocenylethyl substituents are reported [M(CO)5L: M = Cr, Mo, W; L = PH2(CH2CH2Fc), PH(CH2CH2Fc)2, P(CH2CH2Fc)3]. The structure and composition of the complexes were confirmed by multinuclear NMR spectroscopy, IR and UV-Vis absorption spectroscopy, mass spectrometry, X-ray crystallography, and elemental analysis. The solid-state structural data reported revealed trends in M-C and M-P bond lengths that mirrored those of the atomic radii of the Group 6 metals involved. UV-Vis absorption spectroscopy and cyclic voltammetry highlighted characteristics consistent with electronically isolated ferrocene units including wavelengths of maximum absorption between 435 and 441 nm and reversible one-electron (per ferrocene unit) oxidation waves between 10 and -5 mV relative to the ferrocene/ferrocenium redox couple. IR spectroscopy confirmed that the σ donating ability of the phosphines increased as ferrocenylethyl substituents were introduced and that the tertiary phosphine ligand described is a stronger σ donor than PPh3 and a weaker σ donor than PEt3, respectively.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Air-stable primary phosphines were photopolymerized using phosphane–ene chemistry, the phosphorus analogue of the thiol–ene reaction, to fabricate a completely new class of polymer networks. It was demonstrated that the tunable thermal and physical properties accessible using thiol–ene chemistry could also be achieved using an analogous phosphane–ene reaction. At the same time, the presence of the 31P nucleus that is easily observed using NMR spectroscopy allowed the chemical structures of the networks to be directly probed using solid state NMR spectroscopy. Following its incorporation into the network, phosphorus offers the distinct difference and advantage of being able to undergo a diverse array of further derivatization to afford functional materials. For example, the networks were demonstrated to serve as effective oxygen scavengers and to bind transition metals (e.g., Pd). By using the air stable ferrocenyl phosphine (FcCH2CH2)PH2, redox-active networks were produced and these materials could be pyrolyzed to yield magnetic ceramics. Overall, this demonstrates the promise of phosphane–ene chemistry as an alternative to thiol–ene systems for providing functional materials for a diverse range of applications.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
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