Tetravalent cerium pseudohalide complexes supported by the Kläui tripodal ligand [Co(η5-C5H5){P(O)(OEt)2}3]−. Issue 45 (28th October 2016)

• Record Type: Journal Article
• Authors: Au-Yeung, Ka-Chun; So, Yat-Ming; Sung, Herman H.-Y.; Williams, Ian D.; Leung, Wa-Hung
• Is Part Of: Dalton transactions. Volume 45:Issue 45(2016)
• Page Start: 18163
• Page End: 18170
• Publication Date: 2016-10-28
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c6dt03740b
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Cerium(iv ) pseudohalide complexes supported by the Kläui tripodal ligand [Co(η 5 -C5 H5 ){P(O)(OEt)2 }3 ] − (LOEt − ) have been synthesized and structurally characterized. Abstract : Cerium(iv ) pseudohalide complexes supported by the Kläui tripodal ligand [Co(η 5 -C5 H5 ){P(O)(OEt)2 }3 ] − (LOEt − ) have been synthesized and structurally characterized. The treatment of [Ce IV (LOEt )2 Cl2 ] (1 ) with 2 equivalents of [AgX] in acetonitrile afforded [Ce IV (LOEt )2 X2 ] [X − = NCS − (2 ), N3 − (3 ), F − (4 )]. The reaction of1 with [AgCN] in dichloromethane at −40 °C led to formation of a bimetallic Ce IV /Ag I cyanide complex that decomposed in solution at room temperature. In the presence of BPh3, 1 reacted with [AgCN] to yield the cyanoborate complex [Ce IV (LOEt )2 (NCBPh3 )2 ] (6 ) that is stable in solution. The chlorination of [Ce III (LOEt )2 (NO3 )] with PhICl2 afforded [Ce IV (LOEt )2 (NO3 )Cl] (7 ) that reacted with [AgCN] to yield the heterometallic Ce IV /Ag I cyanide complex [{Ce(LOEt )2 (NO3 )}2 {μ-Ag(CN)2 }][AgCl2 ] (8 ). The reaction of [Ce IV (LOEt )Cl3 ] with [AgN3 ] afforded the tetranuclear Ce IV oxo azido cluster [Ce4 (LOEt )4 (μ4 -O)(μ2 -O)2 (μ2 -N3 )6 ] (9 ). The structures of complexes2, 3, 6 and9 have been established by X-ray crystallography.