Premium
Gas‐Phase Fragmentation Reactions of Keggin‐Type {PW 11 O 39 M} (M = Rh, Ir, and Ru) Polyoxometalates as Fingerprints of the Ligands Attached at the Noble Metal Site
Author(s) -
Vicent Cristian,
Adonin Sergey A.,
Anyushin Alexander V.,
Mainichev Dmitry A.,
Sokolov Maxim N.
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402521
Subject(s) - chemistry , thiocyanate , chloride , metal , dissociation (chemistry) , iodide , fragmentation (computing) , inorganic chemistry , alkali metal , medicinal chemistry , organic chemistry , computer science , operating system
The gas‐phase fragmentation reactions of Keggin‐type [PW 11 O 39 MCl] 5– (M = Rh, Ir) polyoxometalates (POMs) featuring chloride terminal ligands have been investigated. Different adducts of the general formulas [PW 11 O 39 MCl + 2cat] 3– and [PW 11 O 39 MCl + 3cat] 2– [cat = alkylammonium cations (Me 4 N + , Bu 4 N + ), alkali cations (Na + , K + ) or protons] were subjected to collision‐induced dissociation (CID) conditions. The (cat)Cl (cat = H + , Na + or K + ) fragments were released as a common fragmentation pathway and were taken as a fingerprint of the ligands attached at the noble metal site. Other {PW 11 O 39 ML} POMs (M = Rh, Ir) with L = thiocyanate, nitrite, methyl, phenylacetate or phenyl were identified on the basis of CID experiments. Coordination studies of thiocyanate anions and CO to {PW 11 O 39 Ru} POMs to yield the new compounds [PW 11 O 39 RuSCN] 5– and [PW 11 O 39 RuCO] 4– are also reported. CID experiments were also used to validate that thiocyanate and CO ligation at the Ru metal site had occurred.