The β-diketiminato nickel(I) complex K2[L(tBu)Ni(I)(N2(2-))Ni(I)L(tBu)] reacts with CO2 via reductive disproportionation to form CO and CO3(2-) containing products, whereas after employment of the Ni(I) precursor [L(tBu)Ni(I)(N2)Ni(I)L(tBu)] reductive coupling of CO2 was observed giving an oxalate bridged dinickel(II) complex. The addition of KC8 to the carbonate and oxalate compounds formed leads to the regeneration of the initial Ni(I) complexes in an N2 atmosphere, thus closing synthetic cycles.

After single electron reduction of the dinitrogen complex [L tBu Ni(μ-η 1 :η 1 -N 2 )NiL tBu ] (I) with KC 8 , reaction of the resulting compound K[L tBu Ni(μ-η 1 :η 1 -N 2 )NiL tBu ] (II) with sodium sand yields KNa[L tBu Ni(μ-η 1 :η 1 -N 2 )NiL tBu ] (1), which contains two different alkali metal ions. Treatment of I with two equivalents of sodium sand leads to the symmetric complex Na 2 [L tBu Ni(μ-η 1 :η 1 -N 2 )NiL tBu ] (2). Complexes 1 and 2 were investigated by single crystal X-ray diffraction analysis as well as by Raman spectroscopy, and the results were compared with the data of K 2 [L tBu Ni(μ-η 1 :η 1 -N 2 )NiL tBu ] (III), which 1169 contains two K + ions. Thus, it became obvious that the nature of the alkali metal ion M in compounds M 2 [L tBu Ni(μ-η 1 :η 1 -N 2 )NiL tBu ] has hardly any influence on the degree of NN bond activation. Furthermore, it was shown that treatment of the dinickel(I) complex III with CO leads to the dinickel(0) compound K 2 [L tBu Ni(CO)] 2 (4) and N 2 . Reaction of the unreduced dinickel(I) complex I with CO leads to a more simple replacement of the N 2 ligand and formation of [L tBu Ni(CO)] (3). Scheme 1.Stepwise reduction of I. [1]

Three-dimensional printing has already been shown to be beneficial to the fabrication of custom-fit and functional products in different industry sectors such as orthopaedics, implantology and dental technology. Especially in personal protective equipment and sportswear, three-dimensional printing offers opportunities to produce functional garments fitted to body contours by directly printing protective and (posture) supporting elements on textiles. In this article, different flexible thermoplastic elastomers, namely, thermoplastic polyurethanes and thermoplastic styrene block copolymers with a Shore hardness range of 67A–86A are tested as suitable printing materials by means of extrusion-based fused deposition modelling. For this, adhesion force, abrasion and wash resistance tests are conducted using various knitted and woven workwear and sportswear fabrics primarily made of cotton, polyester or aramid as textile substrates. Due to polar interactions between thermoplastic polyurethane and textile substrates, excellent adhesion and high fastness to washing is observed. While fused-deposition-modelling-printed polyether-based thermoplastic polyurethane polymers keep their abrasion–resistant properties, polyester-based thermoplastic polyurethanes are more prone to hydrolysis and can be partially degraded if presence of moisture cannot be excluded during polymer processing and printing. Thermoplastic styrene compounds generally exhibit lower adhesion and abrasion resistance, but these properties can be sufficient depending on the requirements of a particular application. Soft thermoplastic styrene filaments can be processed down to a Shore hardness of 70A resulting in three-dimensional printed parts with good quality and comfortable soft-touch surface. Finally, three demonstrator case studies are presented covering the entire process to realize the customized and three-dimensional printed textile. This encompasses product development and fabrication of a textile integrated custom-fit back protector and knee protector as well as customized functionalization of a technical interior textile for improved acoustic comfort. In the future, printing material modifications by compounding processes have to be taken into account for optimized functional performance.

The greenhouse gas sulfur hexafluoride is the common standard example in the literature of a very inert inorganic small molecule that is even stable against O2 in an electric discharge. However, a reduced β-diketiminate nickel species proved to be capable of converting SF6 into sulfide and fluoride compounds at ambient standard conditions. The fluoride product complex features an unprecedented [NiF](+) unit, where the Ni atom is only three-coordinate, while the sulfide product exhibits a rare almost linear [Ni(μ-S)Ni](2+) moiety. The reaction was monitored applying (1)H NMR, IR and EPR spectroscopic techniques resulting in the identification of an intermediate nickel complex that gave insight into the mechanism of the eight-electron reduction of SF6.

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