Treatment of [Rh(µ-Cl)(coe) 2 ] 2 (coe = cyclooctene) with 4,4Ј-di-tert-butyl-2,2Ј-bipyridine (tbbpy) gives the bipyridine complex [Rh(Cl)(tbbpy)(coe)] (1). A subsequent reaction with dihydrogen results in the formation of the cluster [{Rh(Cl)(H)-(tbbpy)}] 4 (2). The reaction of [Rh(µ-Cl)(coe) 2 ] 2 with tbbpy in thf followed by the addition of CNtBu affords [Rh(Cl)(tbbpy)-
A reaction of trans-[Ir(4-C(5)NF(4))(η(2)-C(2)H(4))(PiPr(3))(2)] (1) with an excess of water in THF at room temperature affords the hydrido hydroxo complex trans-[Ir(4-C(5)NF(4))(H)(OH)(PiPr(3))(2)] (2). Treatment of 2 with CO furnishes trans-[Ir(4-C(5)NF(4))(H)(OH)(CO)(PiPr(3))(2)] (3). Reductive elimination of water from 3 leads to the formation of the iridium(I) carbonyl complex trans-[Ir(4-C(5)NF(4))(CO)(PiPr(3))(2)] (4). The insertion of CO(2) into the Ir-O bond of 2 forms the hydrido hydrogencarbonato complex trans-[Ir(4-C(5)NF(4))(H)(κ(2)-(O,O)-O(2)COH)(PiPr(3))(2)] (5). Treatment of 2 with NH(3) in C(6)D(6) yields trans-[Ir(4-C(5)NF(4))(H)(OH)(NH(3))(PiPr(3))(2)] (6). Storage of the reaction mixture at room temperature reveals the formation of the N-H activation product [Ir(4-C(5)NF(4))(H)(μ-NH(2))(NH(3))(PiPr(3))](2) (7).
The first zwitterionic silyl-iridium(v) complex is generated by insertion of silylene into an iridium-hydrogen bond of the iridium(v) hydride , [(eta(5)-C(5)Me(5))IrH(4)]. Complex undergoes proton migration from an IrH moiety to the terminal CH(2) group of the silyl ligand to furnish the N-donor stabilised Ir(iii)-silylene complex .
The hydrido complexes trans-[Pd(H)(4-C(5)NF(4))(PiPr(3))(2)] (3) and trans-[Pd(H)(4-C(5)NF(4))(PCy(3))(2)] (5) can be prepared by reaction of trans-[Pd(F)(4-C(5)NF(4))(PiPr(3))(2)] (2) or trans-[Pd(F)(4-C(5)NF(4))(PCy(3))(2)] (4) with HBpin (HBpin = 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, pinacolborane). The iodo and triflato complexes trans-[Pd(I)(4-C(5)NF(4))(PiPr(3))(2)] (7) and trans-[Pd(OTf)(4-C(5)NF(4))(PiPr(3))(2)] (9) are generated on treatment of complex 3 with MeI or ethyltrifluoromethanesulfonate (EtOTf), respectively. Treatment of 3 with Ph(3)CPF(6) in MeCN results in the formation of trans-[Pd(4-C(5)NF(4))(NCMe)(PiPr(3))(2)]PF(6) (6a). Heating 3 to 60 degrees C gives the products of reductive elimination 2,3,5,6-tetrafluoropyridine as well as [Pd(PiPr(3))(2)] (1). In the presence of pentafluoropyridine [Pd(PiPr(3))(2)] (1) affords the oxidative addition product 2. In a catalytic experiment, pentafluoropyridine can be converted into 2,3,5,6-tetrafluoropyridine in the presence of HBpin with 44% yield when 10% of 3 is employed as catalyst.
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