The thiolate-bridged diiron carbonyl complex [{Fe(μ-PyBPT-κ 3 N,C,S)(CO) 2 }Fe(CO) 3 ] (1) consists of two units, Fe(PyBPT)(CO) 2 and Fe(CO) 3 , where the N,C,S-pincer ligand PyBPT is a doubly deprotonated form of 3′-(2″-pyridyl)-1,1′-biphenyl-2-thiol. The two Fe complex units are connected through a thiolate S atom, π coordination, and an Fe−Fe bond. Diiron complex 1 reacted with 1 equiv of dimethylphenylphosphine to form the CO substitution product [{Fe(μ-PyBPT-(2), which has a polarized Fe−Fe bond. A further reaction of 3 with PMe 2 Ph produced the N,C,S-pincer iron(II) complex trans-[Fe(PyBPT-κ 3 N,C,S)(CO)(PMe 2 Ph) 2 ] (4) and the iron(0) complex trans-[Fe(CO) 3 (PMe 2 Ph) 2 ]. 1,2-Bis(diphenylphosphino)benzene (dppbz) abstracted the Fe(CO) 3 unit from 1 to give the dimeric diiron(II,II) complex [{Fe(μ-PyBPT-κ 3 N,C,S)(CO) 2 } 2 ] (7) and the iron(0) complex [Fe(CO) 3 (dppbz)]. The asymmetric bridging ligand PyBPT and coordination of the phosphines induce polarization of the Fe−Fe bond, which leads to the formation of the iron(II) and iron(0) complexes via heterolytic Fe−Fe cleavage. Electrochemical properties of 3 and 4 were investigated by cyclic voltammetry. Complex 3 showed two one-electron-reduction processes, the potentials of which are ca. 0.4 V more negative than those of 1. Electrocatalytic proton reduction by 3 was investigated, and the efficiency was comparable to that of 1.

A thermal reaction of 6-(4''-dibenzothienyl)-2,2'-bipyridine (bpyDBT) with [Ru(3)(CO)(12)] produced a sulfur-bridged triruthenium complex via double carbon-sulfur bond cleavage and CO insertion, while a diiron(I,I) complex containing a thiametallacycle was obtained by a photochemical reaction of bpyDBT with [Fe(CO)(5)].

CrystEngComm COMMUNICATION Tsunehisa Kimura et al. Single-crystal structure determination from microcrystalline powders (~5 µm) by an orientation attachment mountable on an in-house X-ray diffractometer

A technique for collecting single-crystal X-ray diffraction data using a suspension of microcrystalline powder is reported. The technique developed is based on the three-dimensional alignment of microcrystals by the intermittent rotation of the suspension under static magnetic field, in combination with in situ X-ray measurements. The magnetic attachment required to perform these in situ measurements is significantly simplified because the shutter system equipped with the magnetic system in the previous reported attachment is not necessary in the current technique owing to the application of intermittent rotation. Using this technique, the measurement time is significantly decreased in comparison to that required in our previous procedure. The successful performance of this technique is demonstrated by the structural determination of L-alanine from its microcrystalline powder.

In this study, the magnetically oriented microcrystal suspension (MOMS) method is combined with the shutterless continuous rotation method. In the MOMS method, the suspension has to be rotated to maintain the three‐dimensional orientation of microcrystals. This means that it is compatible with the continuous rotation method, which also utilizes sample rotation. The time constants of the two methods should match to allow their successful combination. The conditions required for the MOMS method for combination with the continuous rotation method are investigated. Experiments are performed with a complementary metal–oxide semiconductor (CMOS) detector and the restriction imposed on the time constant for the MOMS method by the continuous rotation method is examined. The combination of these two methods is a promising approach for realizing the structure analyses of biomolecules from their microcrystalline powders.