Isolation and Structural Characterization of Eightfold Protonated Octacyanometalates [M(CNH)8]4+ (M=MoIV, WIV) from Superacids

2020/03/24 by Malte Sellin, Valérie Marvaud, Moritz Malischewski · 1 citation
Chemistry · Materials Science · #Inorganic Fluorides and Related Compounds #Magnetism in coordination complexes #Inorganic Chemistry and Materials

paper · pdf · doi:10.1002/anie.202002366

openalex publication_date 2020/03/24 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/01

Abstract

Abstract Octacyanometalates K 4 [Mo(CN) 8 ] and K 4 [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+ [SbF 6 ] − 4 and [W(CNH) 8 ] 4+ [SbF 6 ] − 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.

Citations

• Crystal Structure Determination of the Pentagonal‐Pyramidal Hexamethylbenzene Dication C6(CH3)62+
• Emergence of a CNH and cyano complex based organometallic chemistry

Cited by

• Potassium octacyanomolybdate(IV) [wikipedia]

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