Heterolytic H_2 Activation Mediated by Low-Coordinate L_3Fe-(µ-N)-FeL_3 Complexes to Generate Fe(µ-NH)(µ-H)Fe Species

The diiron μ-nitride complexes, {L_3Fe^(II)(μ-N)Fe^(II)L_3}- and L_3Fe^(III)(μ-N)Fe^(II)L_3, heterolytically activate hydrogen (1 atm) at ambient temperature in solution (L_3 = [PhB(CH_2PPh_2)_3]-). These transformations lead to structurally unique {L_3Fe^(II)(μ-NH)(μ-H)Fe^(II)L^3}- and L_3Fe^(III)(μ-NH)(μ-H)Fe^(II)L_3 products. X-ray data establish a marked reduction in the Fe−Fe distance upon H_2 uptake, and spectroscopic data establish both Fe^(II)Fe^(II) species to be diamagnetic, whereas the Fe^(III)Fe^(II) species, L_3Fe^(III)(μ-N)Fe^(II)L_3 and L_3Fe^(III)(μ-NH)(μ-H)Fe^(II)L_3, populate doublet ground states with thermally accessible higher spin states

High-spin and low-spin iron(II) complexes with facially-coordinated borohydride ligands

Rare examples of monometallic high-spin and low-spin L_3Fe(H_3BH) complexes have been characterized, where the two L_3 ligands are [Tp^(Ph2)] and [PhBP3] ([Tp^(Ph2)] = [HB(3,5-Ph_2pz)_3]− and [PhBP_3] = [PhB(CH_2PPh_2)_3]−). The structures are reported wherein the borohydride ligand is facially coordinated to the iron center in each complex. Density functional methods have been employed to explain the bonding in these unusual iron(II) centers. Despite the differences in spin states, short Fe–B distances are observed in both complexes and there is significant theoretical evidence to support a substantial bonding interaction between the iron and boron nuclei. In light of this interaction, we suggest that these complexes can be described as (L_3)Fe(η^4-H_3BH) complexes

Vibrational Spectroscopy and Analysis of Pseudo-tetrahedral Complexes with Metal Imido Bonds

A number of assignments have been previously posited for the metal−nitrogen stretch (ν(M-NR)), the N−R stretch (ν(MN−R)), and possible ligand deformation modes associated with terminally bound imides. Here we examine mononuclear iron(III) and cobalt(III) imido complexes of the monoanionic tridentate ligand [PhBP_(3)] ([PhBP_(3)] = [PhB(CH_(2)PPh_(2))_(3)]^(-)) to clarify the vibrational features for these trivalent metal imides. We report the structures of [PhBP_(3)]Fe≡N^(t)Bu and [PhBP_(3)]Co≡N^(t)Bu. Pseudo-tetrahedral metal imides of these types exhibit short bond lengths (ca. 1.65 Å) and nearly linear angles about the M−N−C linkages, indicative of multiple bond character. Furthermore, these compounds give rise to intense, low-energy visible absorptions. Both the position and the intensity of the optical bands in the [PhBP_(3)]M≡NR complexes depend on whether the substituent is an alkyl or aryl group. Excitation into the low-energy bands of [PhBP_(3)]Fe≡N^(t)Bu gives rise to two Raman features at 1104 and 1233 cm^(-1), both of which are sensitive to ^(15)N and ^(2)H labeling. The isotope labeling suggests the 1104 cm^(-1) mode has the greatest Fe−N stretching character, while the 1233 cm^(-1) mode is affected to a lesser extent by ^(15)N substitution. The spectra of the deuterium-labeled imides further support this assertion. The data demonstrate that the observed peaks are not simple diatomic stretching modes but are extensively coupled to the vibrations of the ancillary organic group. Therefore, describing these complexes as simple diatomic or even triatomic oscillators is an oversimplification. Analogous studies of the corresponding cobalt(III) complex lead to a similar set of isotopically sensitive resonances at 1103 and 1238 cm^(-1), corroborating the assignments made in the iron imides. Very minimal changes in the vibrational frequencies are observed upon replacement of cobalt(III) for iron(III), suggesting similar force constants for the two compounds. This is consistent with the previously proposed electronic structure model in which the added electron resides in a relatively nonbonding orbital. Replacement of the tBu group with a phenyl ring leads to a significantly more complicated resonance Raman spectrum, presumably due to coupling with the vibrations of the phenyl ring. Polarization studies demonstrate that the observed modes have A1 symmetry. In this case, a clearer resonance enhancement of the signals is observed, supporting a charge transfer designation for the electronic transitions. A series of isotope-labeling experiments has been carried out, and the modes with the greatest metal−nitrogen stretching character have been assigned to peaks at 960 and 1300 cm^(-1) in both the iron and cobalt [PhBP_(3)]M≡NPh complexes. These results are consistent with a multiple M−N bond for these metal imides

Protein decorated nano-polystyrene beads: an update about their size and density

The bio-non/bio interfaces is one of the key aspects in the development of nanotechnology applications both for biomedical applications and for understanding their behaviour in the environment where they could contribute to pollution. Protein adsorption onto synthetic polymer nanoparticles, a spontaneous, highly favorable process, is likely a mix of physical (electrostatic, hydrophobic, dispersion, etc.) and chemical interactions (hydrogen bonds, π-π stacking). In this work, we focus on the adsorption of immunoglobulin proteins of type E onto synthetic polymer nanoparticles (polystyrene - PS), a versatile platform for developing imaging and drug delivery applications. PS particles of 100 nm and 196 nm were accurately size characterized with two separation techniques, centrifugal liquid separation (CLS) and centrifugal field flow fraction (CF3), before and after coating them with a layer of antibodies against immunoglobulins of type E (aIgE), giving to the particle a specific functionality. Particle sizes were also measured with Dynamic Light Scattering (DLS), used either as stand-alone instrument and on-line linked CF3 detector (CF3-DLS). The complementary information obtained from the CLS and CF3-DLS measurements allowed the estimation of the density of the aIgE shell. The proteins immobilized at the surface fully retained their activity, as proven by the reactions between the functionalized PS-aIgE particles and immunoglobulins of type E (IgE) dispersed in suspensions prepared on purpose. The aim of this study differed from previous ones since it seeked to compare the capabilities of the two separation techniques, both based on centrifugal field (CLS and CF3), to measure the amount of aIgE adsorbed and to identify the formation of aggregates during the experiments