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Arsenic monophosphide (AsP) species supported by two different N-heterocyclic carbenes were prepared by reaction of (IDipp)PSiMe 3 (1) (IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with (IMes)AsCl 3 (2) (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) to afford the dichloride [(IMes)As(Cl)P(IDipp)]Cl (3), which upon reduction with KC 8 furnished heteroleptic [(IMes)AsP(IDipp)] (4). The corresponding mono- and dications [(IMes)AsP(IDipp)][PF 6 ], [5]PF 6 , and [(IMes)AsP(IDipp)][GaCl 4 ] 2, [6][GaCl 4 ] 2 , respectively, were prepared by one-electron oxidation of 4 with ferrocenium hexafluorophosphate, [Fc]PF 6, or by chloride abstraction from 3 with two equivalents of GaCl 3 , respectively. Compounds 4-6 represent rare examples of heterodiatiomic interpnictogen compounds, and X-ray crystal structure determinations together with density functional theory (DFT) calculations reveal a consecutive shortening of the As-P bond lengths and increasing bond order, in agreement with the presence of an arsenic-phosphorus single bond in 4 and a double bond in 6 2+ . The EPR signal of the cationic radical [5] +. indicates a symmetric spin distribution on the AsP moiety through strong hyperfine coupling with the 75 As and 31 P nuclei., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Chemically inert oxidometal(V) corrols of molybdenum and rhenium undergo clean ligand-exchange reactions upon the action of SiCl 4 . The resulting dichlorido complexes show trigonal prismatic coordination of the metal ion with the chlorine atoms residing in a cis configuration, and were studied by optical and resonance spectroscopy as well as DFT calculations. In situ reactivity studies with carbon nucleophiles indicate high reactivity for chlorine replacement. Treatment with sodium cyclopentadienide paves the way to robust molybdenum corrolocene half-sandwich complexes. These organometallic compounds are the first corrole species that stabilize an air-stable and diamagnetic low spin d 2 -Mo IV center. Structural, spectroelectrochemical, and chemical investigations prove a reversible Mo IV /Mo V redox couple close to the Fc/Fc + potential for these systems. The high stability of the compounds in both redox states calls for future applications in catalysis and as redox switch., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)