[1,2-Bis(diphenyl­phosphino)ethane]{2-[bis­(diphenyl­phosphinometh­yl)amino]pyridinium}fluoridohydrazidato­molybdenum(IV) bis­(tetra­fluoridoborate)

In the crystal structure of the title compound, [MoF(N2H2)(C31H29N2P2)(C26H24P2)](BF4)2, each Mo atom is surrounded by four P atoms of one 1,2-bis­(diphenyl­phosphino)ethane and one 2-[bis­(diphenyl­phosphinometh­yl)amino]pyridinium ligand. The remaining binding sites of the distorted octa­hedron are occupied by a hydrazidate (NNH2 2−) and a fluoride ligand. Two F atoms of an anion are disordered over two positions; the site occupancy factors are ca 0.7 and 0.3

N2 Reduction versus H2 Evolution in a Molybdenum- or Tungsten-Based Small-Molecule Model System of Nitrogenase

Molybdenum dinitrogen complexes have played a major role as catalytic model systems of nitrogenase. In comparison, analogous tungsten complexes have in most cases found to be catalytically inactive. Herein, a tungsten complex was shown to be supported by a pentadentate tetrapodal (pentaPod) phosphine ligand, under conditions of N2 fixation, primarily catalyzes the hydrogen evolution reaction (HER), in contrast to its Mo analogue, which catalytically mediates the nitrogen-reduction reaction (N2 RR). DFT calculations were employed to evaluate possible mechanisms and identify the most likely pathways of N2 RR and HER activities exhibited by Mo- and W-pentaPod complexes. Two mechanisms for N2 RR by PCET are considered, starting from neutral (M(0) cycle) and cationic (M(I) cycle) dinitrogen complexes (M=Mo, W). The latter was found to be energetically more favorable. For HER three scenarios are treated; that is, through bimolecular reactions of early M-Nx Hy intermediates, pure hydride intermediates or mixed M(H)(Nx Hy ) species

Spin-Crossover Molecules on Surfaces: From Isolated Molecules to Ultrathin Films

Molecular spintronics seeks to use single or few molecules as functional building blocks for spintronic applications, directly relying on molecular properties or properties of interfaces between molecules and inorganic electrodes. Spin-crossover molecules (SCMs) are one of the most promising classes of candidates for molecular spintronics due to their bistability deriving from the existence of two spin states that can be reversibly switched by temperature, light, electric fields, etc. Building devices based on single or few molecules would entail connecting the molecule(s) with solid surfaces and understanding the fundamental behavior of the resulting assemblies. Herein, the investigations of SCMs on solid surfaces, ranging from isolated single molecules (submonolayers) to ultrathin films (mainly in the sub-10 nm range) are summarized. The achievements, challenges and prospects in this field are highlighted

[Bis(diphenyl­phosphino)methane-κ2 P,P′][bis­(diphenyl­phosphinometh­yl)diethoxy­silane-κ2 P,P′]bis­(dinitro­gen)­molybdenum(0) benzene 0.7-solvate

In the crystal structure of the title compound, [Mo(C25H22P2)(C30H34O2P2Si)(N2)2]·0.7C6H6, the Mo atoms are coordinated by four P atoms and two N atoms in a distorted octa­hedral mode. The two C atoms of one of the two eth­oxy groups are disordered and were refined using a split model and site-occupation factors of 0.7:0.3. The crystal structure contains a benzene solvent mol­ecule with a site occupation of 70%

Copper-Catalyzed Monooxygenation of Phenols: Evidence for a Mononuclear Reaction Mechanism

The CuI salts [Cu(CH3 CN)4 ]PF and [Cu(oDFB)2 ]PF with the very weakly coordinating anion Al(OC(CF3 )3 )4- (PF) as well as [Cu(NEt3 )2 ]PF comprising the unique, linear bis-triethylamine complex [Cu(NEt3 )2 ]+ were synthesized and examined as catalysts for the conversion of monophenols to o-quinones. The activities of these CuI salts towards monooxygenation of 2,4-di-tert-butylphenol (DTBP-H) were compared to those of [Cu(CH3 CN)4 ]X salts with "classic" anions (BF4- , OTf- , PF6- ), revealing an anion effect on the activity of the catalyst and a ligand effect on the reaction rate. The reaction is drastically accelerated by employing CuII -semiquinone complexes as catalysts, indicating that formation of a CuII complex precedes the actual catalytic cycle. This result and other experimental observations show that with these systems the oxygenation of monophenols does not follow a dinuclear, but a mononuclear pathway analogous to that of topaquinone cofactor biosynthesis in amine oxidase

Kupfer‐katalysierte Monooxygenierung von Phenolen: Evidenz für einen mononuklearen Reaktionsmechanismus

Die CuI-Salze [Cu(CH3CN)4]PF und [Cu(oDFB)2]PF mit dem sehr schwach koordinierenden Anion Al(OC(CF3)3)4− (PF), sowie [Cu(NEt3)2]PF mit dem einzigartigen, linearen Bis-Triethylamin-Komplex [Cu(NEt3)2]+ wurden synthetisiert und als Katalysatoren für die Umwandlung von Monophenolen zu o-Chinonen untersucht. Die Aktivitäten dieser CuI-Salze bei der Monooxygenierung von 2,4-Di-tert-butylphenol (DTBP-H) wurden mit denen der [Cu(CH3CN)4]X-Salze mit “klassischen” Anionen (BF4−, OTf−, PF6−) verglichen, wobei ein Anioneneffekt auf die Aktivität des Katalysators und ein Ligandeneffekt auf die Reaktionsgeschwindigkeit festgestellt wurden. Letztere wird durch den Einsatz von CuII-Semichinon-Komplexen als Katalysatoren drastisch erhöht, was darauf hinweist, dass die Bildung eines CuII-Komplexes dem eigentlichen katalytischen Zyklus vorausgeht. Diese und andere experimentelle Erkenntnisse zeigen, dass die Oxygenierung von Monophenolen mit den oben genannten Systemen nicht einem dinuklearen, sondern einem mononuklearen Weg folgt, analog zur Topachinon-Cofaktor-Biosynthese im Enzym Aminoxidase

Dinuclear Copper(I) Complexes Supported by Bis‐Tridentate N‐Donor‐Ligands: Turning‐On Tyrosinase Activity

Four structurally related bis-tridentate N-donor ligands with either two secondary amine or two imine functions were synthesized, and the corresponding dicopper(I) complexes were investigated as catalysts for the tyrosinase-like conversion of 2,4-di-tert-butylphenol (DTBP-H) to 3,5-di-tert-butylquinone (DTBQ). Notably, the imine systems show evidence for both a μ-η2 : η2-peroxo-dicopper(II) species and catalytic conversion of DTBP-H to DTBQ. Moreover, kinetic studies indicate that a dinuclear copper-oxygen species is involved in the monooxygenation of DTBP-H. In contrast, the amine systems do not show monooxygenase activity. Comparison of the experimentally determined catalytic activities with DFT-optimized geometries of μ-η2 : η2-peroxo-dicopper(II) intermediates suggests that the ligand rigidity of the imine systems allows equatorial attack of the substrate and, thus, subsequent monooxygenation whereas this is not possible in the amine systems due to the fact that no free equatorial positions are available in the μ-peroxo intermediate

Spin crossover in dinuclear iron(ii) complexes bridged by bis-bipyridine ligands: dimer effects on electronic structure, spectroscopic properties and spin-state switching

Inspired by the well-studied mononuclear spin crossover compound [Fe(H2B(pz)2)2(bipy)], the bipyridine-based bisbidentate ligands 1,2-di(2,2′-bipyridin-5-yl)ethyne (ac(bipy)2) and 1,4-di(2,2′-bipyridine-5-yl)-3,5-dimethoxybenzene (Ph(OMe)2(bipy)2) are used to bridge two [Fe(H2B(pz)2)2] units, leading to the charge-neutral dinuclear iron(ii) compounds [{Fe(H2B(pz)2)2}2 μ-(ac(bipy)2)] (1) and [{Fe(H2B(pz)2)2}2 μ-(Ph(OMe)2(bipy)2)] (2), respectively. The spin-crossover properties of these molecules are investigated by temperature-dependent PPMS measurements, Mössbauer, vibrational and UV/Vis spectroscopy as well as X-ray absorption spectroscopy. While compound 1 undergoes complete SCO with T1/2 = 125 K, an incomplete spin transition is observed for 2 with an inflection point at 152 K and a remaining high-spin fraction of 40% below 65 K. The spin transitions of the dinuclear compounds are also more gradual than for the parent compound [Fe(H2B(pz)2)2(bipy)]. This is attributed to steric hindrance between the molecules, limiting intermolecular interactions such as π–π-stacking

Spin Crossover in a Cobalt Complex on Ag(111)

The Co-based complex [Co(H2 B(pz)(pypz))2 ] (py=pyridine, pz=pyrazole) deposited on Ag(111) was investigated with scanning tunneling microscopy at ≈5 K. Due to a bis(tridentate) coordination sphere the molecules aggregate mainly into tetramers. Individual complexes in these tetramers undergo reversible transitions between two states with characteristic image contrasts when current is passed through them or one of their neighbors. Two molecules exhibit this bistability while the other two molecules are stable. The transition rates vary linearly with the tunneling current and exhibit an intriguing dependence on the bias voltage and its polarity. We interpret the states as being due to S=1 /2 and 3 /2 spin states of the Co2+ complex. The image contrast and the orders-of-magnitude variations of the switching yields can be tentatively understood from the calculated orbital structures of the two spin states, thus providing first insights into the mechanism of electron-induced excited spin-state trapping (ELIESST)

Surface cis Effect : Influence of an Axial Ligand on Molecular Self-Assembly

Adding ligands to molecules can have drastic and unforeseen consequences in the final products of a reaction. Recently a surface trans effect due to the weakening of a molecule-surface bond was reported. Here, we show a surface cis effect where an axial ligand at adsorbed transition-metal complexes enables lateral bonding among the molecules. In the absence of this ligand, the intermolecular interaction is repulsive and supramolecular patterns are not observed. Fe-tetramethyl-tetraazaannulene on Au(111) was investigated using low-temperature scanning tunneling microscopy and spectroscopy along with density functional theory calculations. At low coverages, the molecules remain isolated. Exposure to CO leads to axial CO bonding and induces reordering into extended clusters of chiral molecular trimers. The changed self-assembly pattern is due to a CO-induced modification of the molecular structure and the corresponding charge transfer between the molecule and the substrate, which in turn changes the lateral intermolecular forces