Heterobimetallic rhenium nitrido complexes containing the Kläui tripodal ligand [Co(η5-C5H5){P(O)(OEt)2}3]−. Issue 12 (19th February 2015)

• Record Type: Journal Article
• Authors: So, Yat-Ming; Chiu, Wai-Hang; Cheung, Wai-Man; Ng, Ho-Yuen; Lee, Hung Kay; Sung, Herman H.-Y.; Williams, Ian D.; Leung, Wa-Hung
• Is Part Of: Dalton transactions. Volume 44:Issue 12(2015)
• Page Start: 5479
• Page End: 5487
• Publication Date: 2015-02-19
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt00093a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Heterometallic rhenium/iridium and rhenium/rhodium complexes containing the Kläui tripodal ligand have been synthesized and characterized. Abstract : Rhenium nitrido complexes containing the Kläui tripodal ligand [Co(η 5 -C5 H5 ){P(O)(OEt)2 }3 ] − (LOEt − ) have been synthesised and their reactions with [Ir I (cod)Cl]2 (cod = 1, 5-cyclooctadiene) and [Rh II 2 (OAc)4 ] (OAc − = acetate) have been studied. The treatment of [Bu n 4 N][Re VI (N)Cl4 ] with NaLOEt in methanol afforded the Re VI nitride [Re VI (LOEt )(N)Cl(OMe)] (1 ). Reactions of1 with [Ir I (cod)Cl]2 and [Rh II 2 (OAc)4 ] gave the μ-nitrido complexes [(LOEt )(OMe)ClRe VI (μ-N)Ir I (cod)Cl] (2 ) and [Rh II 2 (OAc)4 {(μ-N)Re VI (LOEt )(OMe)Cl}2 ] (4 ), respectively. [(LOEt )Cl(PPh3 )Re V (μ-N)Ir I (cod)Cl] (3 ) and [(LOEt )Cl(PPh3 )Re VI (μ-N)Ir I (cod)Cl][PF6 ] (3 ·PF6 ) have been synthesised from the reactions of [Ir I (cod)Cl]2 with [Re V LOEt (N)Cl(PPh3 )] and [Re VI LOEt (N)Cl(PPh3 )](PF6 ), respectively. Similarly, the redox pair [Rh II 2 (OAc)4 {(μ-N)Re V (LOEt )(PPh3 )Cl}2 ] (5 ) and [Rh II 2 (OAc)4 {(μ-N)Re VI (LOEt )(PPh3 )Cl}2 ](PF6 )2 (5 ·(PF6 )2 ) have been synthesised from the reactions of [Rh2 (OAc)4 ] with [Re V LOEt (N)Cl(PPh3 )] and [Re VI LOEt (N)Cl(PPh3 )](PF6 ), respectively. While [(LOEt )Cl2 Ru VI (μ-N)Ir I (cod)] (6 ) was obtained from [Ru VI (LOEt )(N)Cl2 ] and [Ir I (cod)Cl]2, the interaction between [Ru VI (LOEt )(N)Cl2 ] and [Rh II 2 (OAc)4 ] in CH2 Cl2 is reversible. The crystal structures of complexes2, 3, 3 ·PF6, 5, 5 ·(PF6 )2 and6 have been determined. X-ray crystallography indicates that the nitrido bridges in2, 3, 3 ·PF6 and6 can be described as M N—Ir (M = Re, Ru) showing Ir–N multiple bond character, whereas the interaction between ReN and Rh in5 and5 ·(PF6 )2 is mostly of the donor–acceptor type. The electrochemistry of the Re nitrido complexes has been investigated by cyclic voltammetry.