In order to improve and extend the rare class of tetrahedral mixed main group transition metal compounds, a new synthetic route for the complexes [{CpMo(CO)2}2(μ,η2:η2‐PE)] (E=As (1), Sb (2)) is described leading to higher yields and a decrease in reaction steps. Via this route, also the so far unknown heavier analogues containing AsSb (3 a), AsBi (4) and SbBi (5) ligands, respectively, are accessible. Single crystal X‐ray diffraction experiments and DFT calculations reveal that they represent very rare examples of compounds comprising covalent bonds between two different heavy pnictogen atoms, which show multiple bond character and are stabilised without any organic substituents. A simple one‐pot reaction of [CpMo(CO)2]2 with ME(SiMe3)2 (M=Li, K; E=P, As, Sb, Bi) and the subsequent addition of PCl3, AsCl3, SbCl3 or BiCl3, respectively, give the complexes 1–5. This synthesis is also transferable to the already known homo‐dipnictogen complexes [{CpMo(CO)2}2(μ,η2:η2‐E2)] (E=P, As, Sb, Bi) resulting in higher yields comparable to those in the literature reported procedures and allows the introduction of the bulkier and better soluble Cp′ (Cp′=tert butylcyclopentadienyl) ligand.

The reactivity of cationic electrophiles towards pentaphosphaferrocene [Cp*Fe(ƞ5-P5)] is explored. We report P–E bond formation for electrophiles across the p-block, producing coordination complexes with unprecedented hetero-bispentaphosphole and hetero-pentaphosphole ligands.

Heterogeneous clusters are a widely utilized class of supercomputers assembled from different types of computing devices, for instance CPUs and GPUs, providing a huge computational potential. Programming them in a scalable way exploiting the maximal performance introduces numerous challenges such as optimizations for different computing devices, dealing with multiple levels of parallelism, the application of different programming models, work distribution, and hiding of communication with computation. We utilize the lattice Boltzmann method for fluid flow as a representative of a scientific computing application and develop a holistic implementation for large-scale CPU/GPU heterogeneous clusters. We review and combine a set of best practices and techniques ranging from optimizations for the particular computing devices to the orchestration of tens of thousands of CPU cores and thousands of GPUs. Eventually, we come up with an implementation using all the available computational resources for the lattice Boltzmann method operators. Our approach shows excellent scalability behavior making it future-proof for heterogeneous clusters of the upcoming architectures on the exaFLOPS scale. Parallel efficiencies of more than 90% are achieved leading to 2604.72 GLUPS utilizing 24,576 CPU cores and 2048 GPUs of the CPU/GPU heterogeneous cluster Piz Daint and computing more than 6.8 × 10 9 lattice cells.

The reaction of [Cp′′′Ni(η3‐P3)] (1) with in situ generated phosphenium ions [RR′P]+ yields the unprecedented polyphosphorus cations of the type [Cp′′′Ni(η3‐P4R2)][X] (R=Ph (2 a), Mes (2 b), Cy (2 c), 2,2′‐biphen (2 d), Me (2 e); [X]−=[OTf]−, [SbF6]−, [GaCl4]−, [BArF]−, [TEF]−) and [Cp′′′Ni(η3‐P4RCl)][TEF] (R=Ph (2 f), tBu (2 g)). In the reaction of 1 with [Br2P]+, an analogous compound is observed only as an intermediate and the final product is an unexpected dinuclear complex [{Cp′′′Ni}2(μ,η3:η1:η1‐P4Br3)][TEF] (3 a). A similar product [{Cp′′′Ni}2(μ,η3:η1:η1‐P4(2,2′‐biphen)Cl)][GaCl4] (3 b) is obtained, when 2 d[GaCl4] is kept in solution for prolonged times. Although the central structural motif of 2 a–g consists of a “butterfly‐like” folded P4 ring attached to a {Cp′′′Ni} fragment, the structures of 3 a and 3 b exhibit a unique asymmetrically substituted and distorted P4 chain stabilised by two {Cp′′′Ni} fragments. Additional DFT calculations shed light on the reaction pathway for the formation of 2 a–2 g and the bonding situation in 3 a.

The redox chemistry of the heterobimetallic tripledecker complexes [(Cp*Fe)(Cp'''Co)(μ,η 5 :η 4 -E 5 )] (E = P (1), As (2), Cp* = 1,2,3,4,5-pentamethyl-cyclopentadienyl, Cp''' = 1,2,4-tri-tertbutyl-cyclopentadienyl) and [(Cp'''Co)(Cp'''Ni)(μ,η 3 :η 3 -E 3 )] (E = P (10), As (11)) was investigated. Compound 1 and 2 could be oxidized to the monocations 3 and 4 and further to the dications 5 and 6, while the initially folded cyclo-E 5 ligand planarizes upon oxidation. The reduction leads to an opposite change in the geometry of the middle deck, which is now folded stronger into the direction of the other metal fragment (formation of monoanions 7 and 8). For the arsenic compound 8, a different behavior is found since a fragmentation into an As 6 (9) and As 3 ligand complex occurs.The Co and Ni triple-decker complexes 10 and 11 can be oxidized initially to the heterometallic monocations 12 and 13, which are not stable in solution and convert selectively into the homometallic nickel complexes 14 and 15 and the cobalt complexes 16 and 17. This behavior was further proven by the oxidation of [(Cp'''Co)(Cp''Ni)(μ,η 3 :η 2 -P 3 )] (19, Cp'' = 1,3-di-tertbutyl-cyclopentadienyl) comprising two different Cp ligands. The transfer of {Cp R M} fragments can be suppressed when a {W(CO) 5 } unit is coordinated to the P 3 ligand (20) prior to the oxidation and the mixed cobalt and nickel cation 21 can be isolated. The reduction of 10 and 11 yields the heterometallic monoanions 22 and 23, where no transfer of the {Cp R M} fragments is observed.

Electrophilic functionalisation of [Cp*Fe(h 5-P 5)] (1) yields the first transition-metal complexes of pentaphospholes (cyclo-P 5 R). Silylation of 1 with [(Et 3 Si) 2 (m-H)][B-(C 6 F 5) 4 ] leads to the ionic species [Cp*Fe(h 5-P 5 SiEt 3)][B-(C 6 F 5) 4 ] (2), whose subsequent reaction with H 2 O yields the parent compound [Cp*Fe(h 5-P 5 H)][B(C 6 F 5) 4 ] (3). The synthesis of a carbon-substituted derivative [Cp*Fe(h 5-P 5 Me)][X] ([X] À = [FB(C 6 F 5) 3 ] À (4 a), [B(C 6 F 5) 4 ] À (4 b)) is achieved by methylation of 1 employing [Me 3 O][BF 4 ] and B(C 6 F 5) 3 or a combination of MeOTf and [Li(OEt 2) 2 ][B(C 6 F 5) 4 ]. The structural characterisation of these compounds reveals a slight envelope structure for the cyclo-P 5 R ligand. Detailed NMRspectroscopic studies suggest a highly dynamic behaviour and thus a distinct lability for 2 and 3 in solution. DFT calculations shed light on the electronic structure and bonding situation of this unprecedented class of compounds.

The reactivity of the tetrahedral dipnictogen complexes [{CpMo(CO)2}2(µ,η2:η2-EE')] (E, E' = P, As, Sb, Bi; "Mo2EE'") towards different one-electron oxidation agents is reported. Oxidation with [Thia][TEF] (Thia+ = C12H8S2+; TEF−...

The thermolysis of Cp'''Ta(CO) 4 with white phosphorus (P 4 ) gives access to [{Cp'''Ta} 2 (μ,η 2 : 2 : 2 : 2 : 1 : 1 -P 8 )] (A), representing the first complex containing a cyclooctatetraene-like (COT) cyclo-P 8 ligand. While ring sizes of n > 6 have remained elusive for cyclo-P n structural motifs, the choice of the transition metal, coligand and reaction conditions allowed the isolation of A. Reactivity investigations reveal its versatile coordination behaviour as well as its redox properties. Oxidation leads to dimerization to afford [{Cp'''Ta} 4 (μ 4 ,η 2 : 2