Pentavalent lanthanide nitride-oxides: NPrO and NPrO− complexes with NPr triple bonds. Issue 5 (5th April 2017)

• Record Type: Journal Article
• Authors: Hu, Shu-Xian; Jian, Jiwen; Su, Jing; Wu, Xuan; Li, Jun; Zhou, Mingfei
• Is Part Of: Chemical science. Volume 8:Issue 5(2017)
• Page Start: 4035
• Page End: 4043
• Publication Date: 2017-04-05
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c7sc00710h
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : The neutral molecule NPrO and its anion NPrO − are characterized to be linear pentavalent praseodymium nitride-oxides that possess PrN triple bonds and PrO double bonds. Abstract : The neutral molecule NPrO and its anion NPrO − are produced via co-condensation of laser-ablated praseodymium atoms with nitric oxide in a solid neon matrix. Combined infrared spectroscopy and state-of-the-art quantum chemical calculations confirm that both species are pentavalent praseodymium nitride-oxides with linear structures that contain PrN triple bonds and PrO double bonds. Electronic structure studies show that the neutral NPrO molecule features a 4f 0 electron configuration and a Pr(v ) oxidation state similar to that of the isoelectronic PrO2 + ion, while its NPrO − anion possesses a 4f 1 electron configuration and a Pr(iv ) oxidation state. The neutral NPrO molecule is thus a rare lanthanide nitride-oxide species with a Pr(v ) oxidation state, which follows the recent identification of the first Pr(v ) oxidation state in the PrO2 + and PrO4 complexes ( Angew. Chem. Int. Ed., 2016, 55, 6896). This finding indicates that lanthanide compounds with oxidation states of higher than +IV are richer in chemistry than previously recognized.