1, 2, 3-Triazolylidene ruthenium(ii)-cyclometalated complexes and olefin selective hydrogenation catalysis. Issue 6 (19th November 2014)

• Record Type: Journal Article
• Authors: Bagh, Bidraha; McKinty, Adam M.; Lough, Alan J.; Stephan, Douglas W.
• Is Part Of: Dalton transactions. Volume 44:Issue 6(2015)
• Page Start: 2712
• Page End: 2723
• Publication Date: 2014-11-19
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c4dt03156c
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Silver(i ) 1, 2, 3-triazol-5-ylidenes [(RCH2 C2 N2 (NMe)Ph)2 Ag][AgCl2 ] (R = Ph3a, C6 H2 iPr3 3b, C6 H2 Me3 3c ) and [(PhCH2 C2 N2 (NMe)R)2 Ag][AgCl2 ] (R = C6 H4 Me3d, C6 H4 CF3 3e ) were synthesized and subsequently treated with RuHCl(PPh3 )3 and RuHCl(H2 )(PCy3 )2 to give cyclometallated and Ru-hydride species as the major and minor products, respectively. Abstract : Silver(i ) 1, 2, 3-triazol-5-ylidenes [(RCH2 C2 N2 (NMe)Ph)2 Ag][AgCl2 ] (R = Ph3a, C6 H2 iPr3 3b, C6 H2 Me3 3c ) and [(PhCH2 C2 N2 (NMe)R)2 Ag][AgCl2 ] (R = C6 H4 Me3d, C6 H4 CF3 3e ) were synthesized and subsequently treated with RuHCl(PPh3 )3 and RuHCl(H2 )(PCy3 )2 . The reaction of3a with RuHCl(PPh3 )3 gave RuHCl(PPh3 )2 (PhCH2 C2 N2 (NMe)Ph) (4a1 ) as the minor product and the cyclometalated complex RuCl(PPh3 )2 (PhCH2 C2 N2 (NMe)C6 H4 ) (4a2 ) as the major product. However, similar reaction with3b selectively formed the cyclometalated complex RuCl(PPh3 )2 ((C6 H2 iPr3 )CH2 C2 N2 (NMe)C6 H4 ) (4b2 ). Similarly the silver(i ) triazolylidenes3a and3b were reacted with RuHCl(H2 )(PCy3 )2 ; gave RuHCl(PCy3 )2 (PhCH2 C2 N2 (NMe)Ph) (5a1 ), RuCl(PCy3 )2 (PhCH2 C2 N2 (NMe)C6 H4 ) (5a2 ) and RuCl(PCy3 )2 ((C6 H2 iPr3 )CH2 C2 N2 (NMe)C6 H4 ) (5b2 ), respectively. Species3c, 3d and3e resulted in the cyclometalated complexes (5c2, 5d2 and5e2 ) as the major products as well as the ruthenium-hydride complexes (5c1, 5d1 and5e1 ) as the minor products. The cyclometalated species are derived from the ruthenium-hydride complexes via C(sp 2 )–H activation. These Ru-complexes were shown to act as hydrogenation catalyst precursors for olefinic substrates including those containing a variety of functional groups.