title: Pyridine-based SNS-iridium and -rhodium sulfide complexes, including d8-d8 metal-metal interactions in the solid state.
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.
authors.affiliation: Department of Organic Chemistry, The Weizmann Institute of Science, Rehovot, Israel.
authors.forename: Yulie
authors.initials: Y
authors.lastname: Klerman
authors.forename: Eyal
authors.initials: E
authors.lastname: Ben-Ari
authors.forename: Yael
authors.initials: Y
authors.lastname: Diskin-Posner
authors.forename: Gregory
authors.initials: G
authors.lastname: Leitus
authors.forename: Linda J W
authors.initials: LJ
authors.lastname: Shimon
authors.forename: Yehoshoa
authors.initials: Y
authors.lastname: Ben-David
authors.forename: David
authors.initials: D
authors.lastname: Milstein