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Bis(cyclopentadienyl) Diimido Complexes of Molybdenum and Tungsten [Cp 2 M(NR) 2 ] at the Limit of Pi‐Bond Saturation
Author(s) -
Radius Udo,
Sundermeyer Jörg,
Peters Karl,
von Schnering HansGeorg
Publication year - 2001
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 - 10.1002/1099-0682(200106)2001:6<1617::aid-ejic1617>3.0.co;2-b
Subject(s) - chemistry , cyclopentadienyl complex , molybdenum , ligand (biochemistry) , tungsten , metal , crystallography , pi bond , crystal structure , sigmatropic reaction , saturation (graph theory) , stereochemistry , bond length , inorganic chemistry , catalysis , organic chemistry , bond order , biochemistry , receptor , mathematics , combinatorics
The new imido compounds [(η 5 ‐C 5 H 5 )M(NR) 2 (η 1 ‐C 5 H 5 )] (R = t Bu: M = Mo 2a , W 2b ; R = Mes: M = W 2c ) have been prepared and the crystal structure of 2c has been determined. Three fluxional processes can be detected by variable temperature proton NMR spectroscopic studies of these cyclopentadienyl complexes, namely: (i) rotation of the σ‐C 5 H 5 ligand about the M−C ipso ‐bonding axis, (ii) migration of the metal complex fragment between the carbon atoms of the σ‐bonded C 5 H 5 ligand (metallotropic migration, sigmatropic rearrangement), and (iii) the interconversion of hapticity of σ‐ and π‐bonded C 5 H 5 ligands.