Sigma- versus Pi-coordination in bis-indenyl- and bis-2-methallyl imido 
complexes of hexavalent molybdenum and tungsten: DF-calculations and crystal 
structure analysis

Radius, U.; Sundermeyer, J.; Peters, K.; von Schnering, H. G.

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Sigma- versus Pi-coordination in bis-indenyl- and bis-2-methallyl imido complexes of hexavalent molybdenum and tungsten: DF-calculations and crystal structure analysis

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Peters, K.
Former Scientific Facilities, Max Planck Institute for Solid State Research, Max Planck Society;

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von Schnering, H. G.
Former Departments, Max Planck Institute for Solid State Research, Max Planck Society;

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Citation

Radius, U., Sundermeyer, J., Peters, K., & von Schnering, H. G. (2002). Sigma- versus Pi-coordination in bis-indenyl- and bis-2-methallyl imido complexes of hexavalent molybdenum and tungsten: DF-calculations and crystal structure analysis. Zeitschrift für anorganische und allgemeine Chemie, 628(5), 1226-1235.

Cite as: https://hdl.handle.net/21.11116/0000-000E-E829-F

Abstract

Bis-indenyl and bis-2-methallyl imido complexes
[(C9H7)(2)M(NR)(2)] (M = Mo, W; R = tert-butyl, mesityl) 1 - 4
and [(H3C-C3H4)(2)M(NtBu)(2)] (M = Mo, W) 6, 7 have been
prepared starting from [Mo(NtBu)(2)Cl-2] or [M(NR)(2)Cl2L2] (M
= W, R = tBu, L = py; M = Mo, W, R = Mes, L-2 = dme) and
indenyl lithium or 2-methallyl magnesium bromide, respectively.
According to spectroscopic data and the crystal structure of 4
there are two different coordination modes of the indenyl
ligands, [(eta(3-)C(9)H(7))M(NR)(2)(eta(1)-C9H7)]. in solution
as well as in the solid state. These compounds show fluxional
rearrangements in solution, namely sigma, pi-exchange of
eta(1)- and eta(1)-coordinated ligands. Similar behavior has
been observed for the 2-methallyl complexes 6 and 7 in
solution. In agreement with experimental observations, DF
calculations on models of 6 strongly suggest a (sigma+pi)-
coordination mode of the eta(3)-coordinated ligand.