Diphosphine dioxide complexes of lanthanum and lutetium – The effects of ligand architecture and counter-anion. (5th September 2017)

• Record Type: Journal Article
• Authors: Bannister, Robert D.; Levason, William; Reid, Gillian; Zhang, Wenjian
• Is Part Of: Polyhedron. Volume 133(2017)
• Page Start: 264
• Page End: 269
• Publication Date: 2017-09-05
• Subjects: Diphosphine dioxide -- Lanthanum -- Lutetium -- X-ray structures -- 31P NMR spectroscopy; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2017.04.039
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: The complexes of three diphosphine dioxide ligands with La and Lu salts (Cl, I, PF6 ) are described and their structures and spectroscopic data discussed. Abstract: The reaction of bis(diphenylphosphino)methane dioxide (dppmO2 ) with LaCl3, LaI3 or LaCl3 /[NH4 ][PF6 ] produces [La(dppmO2 )4 ]Y3 (Y = Cl, I, PF6 ) which contain eight-coordinate, distorted square antiprismatic cations. In contrast, LaCl3 or LaCl3 /[NH4 ][PF6 ] and 1, 2-bis(diphenylphosphino)ethane dioxide (dppeO2 ) produce the polymer [LaCl3 (dppeO2 )1.5 ] n, which has a six-coordinate La centre with three mer -chlorides and three Ph2 P(O)CH2 -donors from three different diphosphine dioxide ligands. The bulkier 1, 2-bis(diphenylphosphino)benzene dioxide (PPO2 ) forms [LaCl2 (PPO2 )2 (H2 O)2 ]Cl and [LaCl2 (PPO2 )2 (H2 O)2 ][PF6 ], which contain eight-coordinate La, and also the seven-coordinate [LaCl(PPO2 )3 ][PF6 ]2 . The smaller lutetium ion favours six-coordination in [LuCl2 (dppmO2 )2 ]Cl, [LuI2 (dppmO2 )2 ]I, [LuCl(dppmO2 )2 (H2 O)][PF6 ]2 ·2H2 O, [LuCl2 (PPO2 )2 ]Cl, [LuI2 (PPO2 )2 ]I and [Lu(PPO2 )2 (H2 O)2 ][PF6 ]3 . All complexes were characterised by microanalysis, IR, 1 H and 31 P{ 1 H} NMR spectroscopy. X-ray crystal structures are reported for [La(dppmO2 )4 ]Y3 (Y = I, PF6 ), [LaCl3 (dppeO2 )1.5 ] n, [LaCl2 (PPO2 )2 (H2 O)(EtOH)]Cl and [LaCl(PPO2 )3 ][PF6 ]2 .