VII-G-1 Reactivity of Cationic Phosphenium Complexes of Molybdenum: Migration of OR, SR, and NR₂ on a Tertiary Phosphorus Compound to a Phosphenium Ligand

Yoshitaka YAMAGUCHI, Hiroshi NAKAZAWA (Hiroshima Univ. and IMS), Mitsuru KISHISHITA and Katsuhiko MIYOSHI (Hiroshima Univ.)

[Organometallics 15, 4383 (1996)]

The reaction of a cationic monoaminomonoalkoxy phosphenium complex of Mo, mer-[(bpy)(CO)₃Mo{PN(Me)CH₂CH₂O}]⁺, with a diamino-substituted phosphorus compound, PN(Me)CH₂CH₂NMe(Y) (Y = OMe, OEt, SEt, N(CH₂)₃CH₂), proceeds with substitution for CO and then with the Y group migration to the coordinating phosphenium phosphorus to give [(bpy)(CO)₂{PN(Me)CH₂CH₂O(Y)}Mo-{PN(Me)CH₂CH₂NMe}]⁺, which is also prepared from a cationic diamino phosphenium complex of Mo, mer-[(bpy)(CO)₃Mo{PN(Me)CH₂CH₂NMe}]⁺, and a monoamino-substituted phosphorus compound, PN(Me)CH₂CH₂O(Y), by a simple CO/PN(Me)CH₂CH₂O(Y) substitution. This migration reaction is irreversible. The migration mechanism is also discussed.

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