Reactions of cerium complexes with transition metal nitrides: synthesis and structure of heterometallic cerium complexes containing bridging catecholate ligands. Issue 35 (27th August 2019)

• Record Type: Journal Article
• Authors: Cheung, Wai-Man; Au-Yeung, Ka-Chun; Wong, Kai-Hong; So, Yat-Ming; Sung, Herman H. Y.; Williams, Ian D.; Leung, Wa-Hung
• Is Part Of: Dalton transactions. Volume 48:Issue 35(2019)
• Page Start: 13458
• Page End: 13465
• Publication Date: 2019-08-27
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c9dt02959a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Heterometallic cerium complexes containing bridging catecholate ligands have been synthesized from cerium complexes with Kläui's tripodal ligand and metal catecholates. Abstract : In an attempt to synthesize heterometallic cerium nitrido complexes, we studied the reactions of cerium complexes supported by the Kläui tripodal ligand [Co(η 5 -C5 H5 ){PO(OEt)2 }3 ] − (LOEt − ) with transition-metal nitrides. Whereas no reactions were found between Ce–LOEt complexes and [Ru VI (LOEt )(N)Cl2 ] (2 ), treatment of the Ce(iv ) oxo complex [Ce IV (LOEt )2 (O)(H2 O)]·MeCONH2 (1 ) with2 resulted in reduction of both the Ce(iv ) and Ru(vi ) complexes, and formation of a heterometallic Ce(iii )/Ru(iii ) complex with a bridging deprotonated acetamide ligand, [(LOEt )2 (H2 O)Ce III {μ-O, N-MeC(O)NH}Ru III (LOEt )Cl2 ] (4 ), along with a minor product, [Ce III (LOEt )2 (NO3 )]. Ce(iv )–LOEt complexes such as [Ce IV (LOEt )2 Cl2 ] (3 ) can oxidize [Re V (LOEt )(N)(PPh3 )Cl] to give the Re(vi ) nitride [Re VI (LOEt )(N)(PPh3 )Cl] + . Chloride abstraction of3 by TlPF6 followed by reaction with [PPh4 ]2 [Mn V (N)(CN)4 ] afforded a diamagnetic red solid that is tentatively formulated as a heterometallic Ce(iv )/Mn(v ) complex, [Ce(LOEt )2 (H2 O){Mn(N)(CN)4 }] (5 ). Reactions of3 with [ n Bu4 N][M VI (N)(cat)2 ] (cat 2− = catecholate(2−)) afforded the Ce(iii )/M(vi ) complexes [(LOEt )2 Ce III {(μ-cat)2 M VI (N)}] [M = Ru (6 ), Os (7 )], in which the Ce(iii ) and M(vi ) centers are bridged by two oxygen atoms of the two catecholate ligands. Similarly, the catecholate-bridged Ce(iii )/Re(v ) complex [(LOEt )2 Ce III {(μ-cat)2 Re V (O)}] (8 ) was prepared from3 and [Me4 N][Re V (O)(cat)2 ]. In CH2 Cl2, 8 was air-oxidized to the Ce(iii )/Re(vii ) complex [Ce III (LOEt )2 (H2 O)2 ][ cis -{Re VII (O)2 (cat)2 }] (9 ) with a cis -dioxo-Re(vii ) counter-anion. The crystal structures of4, 6, and9 have been determined.