Pyridine-based SNS-iridium and -rhodium sulfide complexes, including d 8-d8 metal-metal interactions in the solid state

Yulie Klerman, Eyal Ben-Ari, Yael Diskin-Posner, Gregory Leitus, Linda J.W. Shimon, Yehoshoa Ben-David, David Milstein

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Abstract

The cationic, pincer-type complexes [(SNS)Ir(COE)][BF4] (1) and [(SNS)Rh(COE)][BF4] (2) (SNS = 2,6-bis(t-butylthiomethy1)pyridine; COE = cyclooctene) complexes were prepared, and their structure and reactivity were studied. They are fluxional at room temperature as a result of "arm" hemilability, which can be frozen at low temperatures. Reaction of complex 1 with H2 resulted in a dimeric dihydride complex [(SNS)Ir(H2)]2[BF4]2 (3) in which the sulfur atoms bridge between two metal centers. The Rh complex 2 did not react with H2. Both the carbonyl complexes [(SNS)Ir(CO)][BF 4] (5) and [(SNS)Rh(CO)][BF4] (6) show differences in the IR stretching frequencies in solution vs. solid states, which are a result of uncommon metal-metal interactions between square planar d8 systems in the solid state. Complexes 1, 3, 5 and 6 were structurally characterized by X-ray crystallography. A network of hydrogen bonds involving the BF 4- counter anion and hydrogen atoms of complex 5 was observed.

Original languageEnglish
Pages (from-to)3226-3234
Number of pages9
JournalDalton Transactions
Issue number24
DOIs
Publication statusPublished - Jun 17 2008

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ASJC Scopus subject areas

  • Inorganic Chemistry

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