Comprehensive Organometallic Chemistry 3ed Vol 01 by D M P Mingos; Robert H Crabtree

By D M P Mingos; Robert H Crabtree

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The fact that the electron needs to occupy an unoccupied orbital means that molecules of the type [MLn]xÀ are only likely to be feasible if the ligand has an empty orbital of sufficiently low energy. e. LZ9), is much more likely to afford anionic [MLn]xÀ derivatives than would PMe3. In support of this statement, [Fe(CO)4]2À has been widely investigated, whereas [Fe(PMe3)4]2À is unknown, despite the fact that the neutral isoelectronic counterpart Ni(PMe3)4 has been synthesized. Applying the transformation LÀ !

In Organometallic Chemistry; Prentice-Hall: New Jersey, 1996, p 44. 13. For specific examples, see: a. Andre´a, R. ; Teuben, J. H. J. Organomet. Chem. 1986, 307, 307–317. b. ; Samuel, E. Inorg. Chem. 1988, 27, 3018–3024. c. ; Kunkely, H. Coord. Chem. Rev. 2004, 248, 273–278. 14a. Collman, J. ; Hegedus, L. ; Norton, J. ; Finke, R. G. In Principles and Applications of Organotransition Metal Chemistry; University Science Books: Mill Valley, Califorinia, 1987, p 26. b. Crabtree, R. H. In The Organometallic Chemistry of the Transition Metals, 4th edition; Wiley: New York, 2005, p 43.

Acceptor functions, however, minimize this charge buildup and thus Mo(CO)6 is more stable than Mo(NH3)6. Molecules that have [MLlXxZz] classifications that are remote from the highly populated areas in an MLX plot are necessarily of considerable interest because of their uniqueness. g. 107 This corresponds to a most unusual valence state for scandium, and the ability to isolate Classification of Organotransition Metal Compounds Electron Number Fe 10 0 11 ML 12 13 ML2 1 MLX 14 15 ML3 ML2X 16 17 18 ML4 ML5 <1% 20% ML3X ML4X <1% 2 MX2 MLX2 3 MX3 ML2X2 ML3X2 ML4X2 <1% <1% 71% MLX3 ML2X3 ML3X3 Valence <1% 4 MX2Z MX4 MLX4 ML2X4 ML3X4 <1% 5 6 MX3Z MX2Z2 7% MX5 MX4Z MLX5 MX6 ML2X5 MLX6 ML2X6 <1% 7 8 MX3Z2 MX2Z3 MX5Z MX4Z2 MX7 MX6Z MLX7 MX8 MLX8 <1% Figure 34 MLX plot for organometallic iron compounds.

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