Pyridine-based SNS-iridium and -rhodium sulfide complexes, including d8–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)][BF4] (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 BF4 counter anion and hydrogen atoms of complex 5 was observed.

Original languageEnglish
Pages (from-to)3226-3234
Number of pages9
JournalJournal of the Chemical Society. Dalton Transactions
Issue number24
DOIs
Publication statusPublished - May 14 2008

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Iridium
Rhodium
Sulfides
Carbon Monoxide
Atoms
X ray crystallography
Sulfur
Stretching
Anions
Hydrogen
Hydrogen bonds
Metals
Temperature
pyridine

ASJC Scopus subject areas

  • Chemistry(all)

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Pyridine-based SNS-iridium and -rhodium sulfide complexes, including d8–d8 metal–metal interactions in the solid state. / Klerman, Yulie; Ben-Ari, Eyal; Diskin-Posner, Yael; Leitus, Gregory; Shimon, Linda J.W.; Ben-David, Yehoshoa; Milstein, David.

In: Journal of the Chemical Society. Dalton Transactions, No. 24, 14.05.2008, p. 3226-3234.

Research output: Contribution to journalArticle

Klerman, Yulie ; Ben-Ari, Eyal ; Diskin-Posner, Yael ; Leitus, Gregory ; Shimon, Linda J.W. ; Ben-David, Yehoshoa ; Milstein, David. / Pyridine-based SNS-iridium and -rhodium sulfide complexes, including d8–d8 metal–metal interactions in the solid state. In: Journal of the Chemical Society. Dalton Transactions. 2008 ; No. 24. pp. 3226-3234.
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