Octahedral Molybdenum(0) Monodinitrogen Complexes Facially Coordinated by the Tripodal Ligand 1,1,1‐Tris(diphenylphosphanylmethyl)ethane – Influence of Diphosphane Coligands on the Activation of N2
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Media type:
E-Article
Title:
Octahedral Molybdenum(0) Monodinitrogen Complexes Facially Coordinated by the Tripodal Ligand 1,1,1‐Tris(diphenylphosphanylmethyl)ethane – Influence of Diphosphane Coligands on the Activation of N2
Published in:
European Journal of Inorganic Chemistry, 2011 (2011) 28, Seite 4377-4386
Language:
English
DOI:
10.1002/ejic.201100640
ISSN:
1434-1948;
1099-0682
Origination:
Footnote:
Description:
AbstractThe synthesis and physicochemical properties of the new molybdenum dinitrogen complexes [Mo(N2)(tdppme)(dmpm)] (2) and [Mo(N2)(tdppme)(dppm)] (3) are reported. Complexes 2 and 3 are facially coordinated by the tripodal ligand 1,1,1‐tris(diphenylphosphanylmethyl)ethane (tdppme) and contain the bidentate coligands bis(dimethylphosphanyl)methane (dmpm) and bis(diphenylphosphanyl)methane (dppm), respectively. They are accessible by amalgam reduction of the MoIII precursor [MoBr3(tdppme)] (1) under nitrogen in the presence of dppm and dmpm, respectively. Protonation of 2 with trifluoromethanesulfonic acid (triflic acid, HOTf) leads to the NNH2 complex [Mo(NNH2)(tdppme)(dmpm)](OTf)2 (4) with retention of the pentaphosphane coordination. The structural, electronic and vibrational properties of 2, 3 and 4 have been investigated by NMR, IR and Raman spectroscopy coupled with DFT calculations. The crystal structure of 2 has been determined and is discussed in relation to the calculated structures of 2 and 3. The results of the investigations are compared with those obtained earlier for the pentaphosphane complexes [Mo(N2)(dpepp)(dppm)] and [Mo(NNH2)(dpepp)(dppm)](OTf)2 [dpepp = bis(diphenylphosphanylethyl)phenylphosphane].