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Bonding interactions between the iron and the porphyrin macrocycle of five- and six-coordinate high-spin iron(III)-porphyrin complexes are analyzed within the framework of approximate density functional theory with the use of the quantitative energy decomposition scheme in combination with removal of the vacant pi orbitals of the porphyrin from the valence space. Although the relative extent of the iron-porphyrin interactions can be evaluated qualitatively through the spin population and orbital contribution analyses, the bond strengths corresponding to different symmetry representations can be only approximated quantitatively by the orbital interaction energies. In contrast to previous suggestions, there are only limited Fe --> P pi back-bonding interactions in high-spin iron(III)-porphyrin complexes. It is the symmetry-allowed bonding interaction between d(z)2 and a(2u) orbitals that is responsible for the positive pi spin densities at the meso-carbons of five-coordinate iron(III)-porphyrin complexes. Both five- and six-coordinate complexes show significant P --> Fe pi donation, which is further enhanced by the movement of the metal toward the in-plane position for six-coordinate complexes. These bonding characteristics correlate very well with the NMR data reported experimentally. The extraordinary bonding interaction between d(z)2 and a(2u) orbitals in five-coordinate iron(III)-porphyrin complexes offers a novel symmetry-controlled mechanism for spin transfer between the axial ligand sigma system and the porphyrin pi system and may be critical to the electron transfer pathways mediated by hemoproteins.

Policies regarding alcohol use have become more flexible particularly toward patients with AAH. Marijuana use is also more accepted. Although policies regarding alcohol and marijuana have changed significantly in the last decade, they remain highly variable among programs.

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An amino-linked nitrogen heterocyclic carbene (amino-NHC), 1-tBu, has been shown to mediate carbon-carbon coupling through the direct C-H functionalization of benzene and pyridine in the absence of a metal catalyst. Using EPR, the first spectroscopic evidence corroborating the single electron transfer mechanism for the metal-free carbon-carbon coupling manifold, as reported by others, is introduced.

This paper describes the design of millimeter-wave wide-band monolithic GaAs passive high electron-mobility transistor (HEMT) switches using the traveling-wave concept. This type of switch combined the off-state shunt transistors and series microstrip lines to form an artificial transmission line with 50-characteristic impedance. A 15-80-GHz single-pole double-throw (SPDT) switch in conjunction with quarter-wavelength impedance transformers demonstrates an insertion loss of less than 3.6 dB and an isolation of better than 25 dB. Another type of wide-band switch was designed by using a series HEMT switch to replace the quarter-wavelength transformer, and the operating band can be extended to dc. With this scheme, dc-80-GHz single-pole single-throw (SPST) and dc-60-GHz SPDT switches are also developed with compact chip size. From dc to 80 GHz, the insertion loss and isolation of the SPST switch are better than 3 and 24 dB, respectively. The SPDT switch has an insertion loss of better than 3 dB and an isolation of better than 25 dB from dc to 60 GHz. The analysis of circuit characteristics and design procedures are also included. It is concluded that the device periphery can be selected for the desired bandwidth, while the number of transistors is decided to achieve the isolation.Index Terms-High electron-mobility transistor (HEMT), switch, traveling wave.

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