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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-AE6B-7
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.