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Synthesis and Protonation Studies of Molybdenum(0) Bis(dinitrogen) Complexes Supported by Diphosphine Ligands Containing Pendant Amines
Author(s) -
Labios Liezel A.,
Weiss Charles J.,
Egbert Jonathan D.,
Lense Sheri,
Bullock R. Morris,
Dougherty William G.,
Kassel W. Scott,
Mock Michael T.
Publication year - 2015
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.201400119
Subject(s) - protonation , chemistry , triflic acid , molybdenum , trifluoromethanesulfonate , medicinal chemistry , hydride , nuclear magnetic resonance spectroscopy , molecule , stereochemistry , catalysis , inorganic chemistry , organic chemistry , metal , ion
A series of molybdenum bis(dinitrogen) complexes of the formula trans ‐[Mo(N 2 ) 2 (P Et N R P Et ) 2 ] (P Et N R P Et = Et 2 PCH 2 N( R )CH 2 PEt 2 ; R = phenyl ( 1 ), 2,6‐difluorobenzyl ( 2 ), 3,5‐difluorobenzyl ( 3 ), CH 2 CH 2 NMe 2 ( 4 ), CH 2 ‐ o ‐Py ( 5 )] were synthesized and characterized by NMR and IR spectroscopy, and X‐ray crystallography. Protonation studies with stoichiometric amounts of triflic acid (HOTf) were performed, and the protonated products were characterized by NMR and in situ IR spectroscopic methods. Products formed in the stepwise protonation reactions included, for example, a mixture of the seven‐coordinate molybdenum bis(dinitrogen) hydride, trans ‐[Mo(H)(N 2 ) 2 (P Et N Ph P Et ) 2 ] + [1H] + , and the Mo‐hydrazido triflate complex, trans ‐[Mo(NNH 2 )(OTf)(P Et N Ph P Et ) 2 ] + [1(NNH 2 )] + . Complex 2 , with more basic pendant amines, can be protonated up to three times, affording the highly‐charged molecule, trans ‐[Mo(H)(N 2 ) 2 (P Et N 2,6‐F2‐Bn (H)P Et ) 2 )] 3+ [2H(PN(H)P) 2 ] 3+ .