Coupling of terminal iridium nitrido complexes. Issue 4 (22nd January 2016)

• Record Type: Journal Article
• Authors: Abbenseth, Josh; Finger, Markus; Würtele, Christian; Kasanmascheff, Müge; Schneider, Sven
• Is Part Of: Inorganic chemistry frontiers. Volume 3:Issue 4(2016)
• Page Start: 469
• Page End: 477
• Publication Date: 2016-01-22
• Subjects: Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5qi00267b
• Languages: English
• ISSNs: 2052-1553

Abstract

Abstract : The homo- and heterocoupling of molecular terminal iridium(iv ) and iridium(v ) nitrides is examined. The experimental coupling rates are discussed based on a computational analysis of the transition states. Abstract : The oxidative coupling of nitride ligands (N 3− ) to dinitrogen and its microscopic reverse, N2 -splitting to nitrides, are important elementary steps in chemical transformations, such as selective ammonia oxidation or nitrogen fixation. Here an experimental and computational evaluation is provided for the homo- and heterocoupling of our previously reported iridium(iv ) and iridium(v ) nitrides [IrN(PNP)] n ( n = 0, +1; PNP = N(CHCHPtBu2 )2 ). All three formal coupling products [(PNP)IrN2 Ir(PNP)] n ( n = 0–+2) were structurally characterized. While the three coupling reactions are all thermodynamically feasible, homocoupling of [IrN(PNP)] + is kinetically hindered. The contributing parameters to relative coupling rates are discussed providing qualitative guidelines for the stability of electron rich transition metal nitrides.