Synthesis and reactivity of rare-earth metal phosphaethynolates. Issue 37 (29th August 2018)

• Record Type: Journal Article
• Authors: Bestgen, Sebastian; Chen, Qien; Rees, Nicholas H.; Goicoechea, Jose M.
• Is Part Of: Dalton transactions. Volume 47:Issue 37(2018)
• Page Start: 13016
• Page End: 13024
• Publication Date: 2018-08-29
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt03427c
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The reactivity and coordination behaviour of OCP − towards three rare-earth elements: Y, Nd and Sm, was investigated. Mono- and bis-phosphaethynolate complexes in different oxidation states were prepared, leading to novel coordination modes of OCP − and ionic intermediates of Sm(ii ) in the presence of 18-crown-6 or 2, 2, 2-crypt. Abstract : Over the course of the last six years, research on the synthesis and reactivity of molecular metal phosphaketenes (M–PCO) has gained increasing attention. However, lanthanide complexes of the heavier group 15 cyanate analogue PCO − have not been investigated so far. Herein we present exemplar studies on the nature and reactivity of rare-earth phosphaethynolato-complexes using three characteristic representatives of the rare-earth metals: Y, Nd and Sm. Our investigations comprise both +2 and +3 redox states, and one defined amidinate-based ligand set, as well as novel reaction pathways in the presence of the sequestering agents 18-crown-6 and 2, 2, 2-crypt.