Keggin-type polyoxometalates [PW11O39MCl] 5- with noble metals (M = Rh and Ir): Novel synthetic entries and ESI-MS directed reactivity screeningстатья
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Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 7 марта 2019 г.
Авторы:
Sokolov M.N. ,
Adonin S.A. ,
Sinkevich P.L. ,
Vicent C. ,
Mainichev D.A. ,
Fedin V.P.
Журнал:
Zeitschrift für anorganische und allgemeine Chemie
Том:
640
Номер:
1
Год издания:
2014
Издательство:
Wiley - V C H Verlag GmbbH & Co.
Местоположение издательства:
Germany
Первая страница:
122
Последняя страница:
127
DOI:
10.1002/zaac.201300287
Аннотация:
A new synthetic entry to iridium Keggin-type polyoxometalate complexes from [PW11O39]7- and K3[IrCl 6] under harsh conditions is reported. The complex [PW 11O39IrCl]5- (15-) featuring an IrCl functionality was obtained in high yield and characterized by NMR spectroscopic and ESI-MS techniques. The presence of Li+ (3-4 M) is essential for a quantitative yield of 15-. The reactivities of 15- and its rhodium analogue [PW11O39RhCl]5- in ligand substitution at the noble metal site were studied. Thiocyanate coordination successfully yielded (Bu4N)5[PW11O 39M(SCN)] [M = Rh (2a), Ir, (3a)]. In both cases, the SCN ligands are coordinated by sulfur atoms, according to 13C NMR and IR spectroscopic data. Gas-phase fragmentation reactions of compounds 2a and 3a were also investigated by collision-induced dissociation (CID) experiments. Reaction of [PW11O39RhCl]5- with NaN 3 resulted in Cl- to OH- replacement accompanied by the liberation of the RhCl fragment, whereas 15- proved unreactive with NaN3. Attempts to coordinate NO 2- are adversely affected by competing noble metal excision with formation of free [PW11O39]7-. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Добавил в систему:
Адонин Сергей Александрович