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(Dinitrogen)molybdenum Complexes Supported by Asymmetric Silicon‐Centered Tripod Ligands: Steric and Electronic Influences on the Coordination of Mono‐ and Diphosphine Coligands
Author(s) -
Broda Henning,
Krahmer Jan,
Tuczek Felix
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402273
Subject(s) - chemistry , steric effects , molybdenum , phosphine , tripod (photography) , nuclear magnetic resonance spectroscopy , stereochemistry , methane , medicinal chemistry , inorganic chemistry , organic chemistry , catalysis , physics , optics
A reliable and generally applicable synthetic route for the rational synthesis of silicon‐centered tripod ligands with mixed dialkylphosphine/diarylphosphine donors is developed. On the basis of this protocol, two new asymmetric SiPPP′ ligands, SiP Me 2 P Ph and SiP Me 2 P i Pr , were prepared and employed for the synthesis of (dinitrogen)molybdenum complexes of the types [Mo(N 2 )(SiPPP′)(P 2 )] [P 2 = (diphenylphosphino)methane (dppm), (dimethylphosphino)methane (dmpm), or two PMe 2 Ph] and [Mo(N 2 ) 2 (SiPPP′)(PMe 2 Ph)]. The constitution of the complexes is elucidated by 31 P NMR spectroscopy and analyzed on the basis of steric and electronic factors. The activation of N 2 in the synthesized dinitrogen complexes is determined by IR spectroscopy and correlated with the donor/acceptor properties of the phosphine coligands.