New examples of Arbuzov rearrangements of coordinated phosphites initiated by metal-centred radicals

Article abstract of DOI:10.1016/0022-328X(95)05888-V

Reaction of the persistent, iron-centred radical {η⁵-C₅Ph₄(p-tolyl)}Fe(CO)₂ · with tertiary phosphites P(OR)₃ (R = Me, Et) results in the formation of the Arbuzov rearrangement products {η⁵-C₅Ph₄(p-tolyl)}Fe(CO)₂R, {η⁵-C₅Ph₄(p-tolyl)}Fe(CO)₂{PO(OR)₂} and {η⁵-C₅Ph₄(p-tolyl)}Fe(CO){P(OR)₃}{PO(OR)₂}. For both phosphites, the metal-centred radicals {η⁵-C₅Ph₄(p-tolyl)}Fe(CO){P(OR)₃} · appear to be intermediates in a process which involves initial, direct abstraction by {η⁵-C₅Ph₄(p-tolyl)}Fe(CO)₂ · of an alkyl group R from the coordinated P(OR)₃ of {η⁵-C₅Ph₄(p-tolyl)}Fe(CO){P(OR)₃} ·, followed by interception of the 16-electron intermediate, {η⁵-C₅Ph₄(p-tolyl)}Fe(CO){PO(OR)₂}, by CO and P(OR)₃.