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Bonding and Activation of N 2 in Molybdenum(0) Complexes Supported by Tripod Ligands with Phospholane End Groups
Author(s) -
Pfeil Mareike,
Engesser Tobias A.,
Krahmer Jan,
Näther Christian,
Tuczek Felix
Publication year - 2021
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.202100166
Subject(s) - denticity , molybdenum , chemistry , protonation , ligand (biochemistry) , tripod (photography) , stereochemistry , medicinal chemistry , crystallography , crystal structure , inorganic chemistry , receptor , ion , biochemistry , physics , organic chemistry , optics
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 MoX 3 (X=Cl, Br, I) complexes supported by these ligands. Na x Hg reduction of [MoBr 3 ( trpd‐3 pln )], in the presence of N 2 and the bidentate coligand dppm leads to the molybdenum(0) mono(dinitrogen) complex [Mo(N 2 )( trpd‐3 pln )(dppm)] with a moderately activated N 2 ligand. An attempt to further increase the activation by using dmpm as coligand leads to a mixture containing desired [Mo(N 2 )( trpd‐3 pln )(dmpm)], but also the bis(dinitrogen) complex [Mo(N 2 ) 2 ( κ 2 ‐ trpd‐3 pln ) 2 ] and the homoleptic complex [Mo( trpd‐3 pln ) 2 ]. Protonation of [Mo(N 2 )( trpd‐3 pln )(dppm)] with [H(OEt 2 ) 2 ][Al{OC(CF 3 ) 3 } 4 ] generates the hydrazido(2‐) complex [Mo(NNH 2 )( trpd‐3 pln )(dppm)][Al{OC(CF 3 ) 3 } 4 ] 2 .