Bonding and Activation of N2 in Molybdenum(0) Complexes Supported by Tripod Ligands with Phospholane End Groups. Issue 18 (22nd July 2021)

• Record Type: Journal Article
• Authors: Pfeil, Mareike; Engesser, Tobias A.; Krahmer, Jan; Näther, Christian; Tuczek, Felix
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 647:Issue 18(2021)
• Page Start: 1778
• Page End: 1788
• Publication Date: 2021-07-22
• Subjects: Nitrogen Fixation -- Phospholane -- tripod ligands -- Molybdenum Complexes; Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.202100166
• Languages: English
• ISSNs: 0044-2313

Abstract

Abstract: Tripod ligands with a neopentyl backbone and one (trpd‐1 pln ), two (trpd‐2 pln ) or three (trpd‐3 pln ) phospholane end groups are synthesized and used for the synthesis of MoX3 (X=Cl, Br, I) complexes supported by these ligands. Nax Hg reduction of [MoBr3 (trpd‐3 pln )], in the presence of N2 and the bidentate coligand dppm leads to the molybdenum(0) mono(dinitrogen) complex [Mo(N2 )(trpd‐3 pln )(dppm)] with a moderately activated N2 ligand. An attempt to further increase the activation by using dmpm as coligand leads to a mixture containing desired [Mo(N2 )(trpd‐3 pln )(dmpm)], but also the bis(dinitrogen) complex [Mo(N2 )2 ( κ2 ‐trpd‐3 pln )2 ] and the homoleptic complex [Mo(trpd‐3 pln )2 ]. Protonation of [Mo(N2 )(trpd‐3 pln )(dppm)] with [H(OEt2 )2 ][Al{OC(CF3 )3 }4 ] generates the hydrazido(2‐) complex [Mo(NNH2 )(trpd‐3 pln )(dppm)][Al{OC(CF3 )3 }4 ]2 . Abstract :