1. Isolation and structural characterization of eightfold protonated octacyanometalates [M(CNH)8]4+ (M=MoIV, WIV) from superacids
- Author
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Sellin, Malte, Marvaud, Valérie, and Malischewski, Moritz
- Subjects
isocyanide ligands ,500 Naturwissenschaften und Mathematik::540 Chemie::546 Anorganische Chemie ,superacidic systems ,Communication ,protonation ,hydrogen bonds ,cyanides ,Communications ,Cyanometalates - Abstract
Octacyanometalates K4[Mo(CN)8] and K4[W(CN)8] are completely protonated in superacidic mixtures of anhydrous hydrogen fluoride and antimony pentafluoride. The resulting hydrogen isocyanide complexes [Mo(CNH)8]4+ [SbF6]− 4 and [W(CNH)8]4+ [SbF6]− 4 are the first examples of eight‐coordinate homoleptic metal complexes containing hydrogen isocyanide (CNH) ligands. The complexes were crystallographically characterized, revealing hydrogen‐bonded networks with short N⋅⋅⋅H⋅⋅⋅F contacts. Low‐temperature NMR measurements in HF confirmed rapid proton exchange even at −40 °C. Upon protonation, ν(C≡N) increases of about 50 cm−1 which is in agreement with DFT calculations., Give me eight! All eight cyano groups in the octacyanometalates Mo(CN)8 4− and W(CN)8 4− are protonated under superacidic conditions without formation of HCN. Instead homoleptic complexes of Mo4+ and W4+ with eight hydrogen isocyanide ligands are formed and could be fully characterized.
- Published
- 2020
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