Title:
Isolation and structural characterization of eightfold protonated octacyanometalates [M(CNH)8]4+ (M=MoIV, WIV) from superacids
Author(s):
Sellin, Malte; Marvaud, Valérie; Malischewski, Moritz
Year of publication:
2020
Available Date:
2020-06-16T13:46:19Z
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.
Part of Identifier:
e-ISSN (online): 1521-3757
Keywords:
cyanides
hydrogen bonds
isocyanide ligands
protonation
superacidic systems
DDC-Classification:
546 Anorganische Chemie
Publication Type:
Wissenschaftlicher Artikel
URL of the Original Publication:
DOI of the Original Publication:
Journaltitle:
Angewandte Chemie
Department/institution:
Biologie, Chemie, Pharmazie
Institut für Anorganische Chemie
Comments:
Die Publikation wurde von der Freien Universität Berlin finanziert.