Haloalkyl complexes of the transition metals. Part 3. Reactions of some chloromethyl and methoxymethyl complexes of molybdenum, tungsten, manganese, rhenium, iron, and ruthenium with some tertiary phosphine and related ligands

Abstract

Die Reaktionen einiger Chlormethyl‐Übergangsmetallkomplexe mit Triphenylphosphin werden in Methanol oder Acetonitril untersucht.

Oxidative Addition of Haloalkanes to Metal Centers: A Mechanistic Investigation

“…Thus, it is likely that the radicals have not diffused out of the cage in the transition state and that therefore recombination is faster than the reaction of either of the radicals with TEMPO. Similar results were previously reported in oxidative addition reactions of alkyl halides to CpW(CO) 3 . A radical mechanism for dichloromethane oxidative addition to other metal centers has been reported as well …”

Reaction of [(1-H-Hydronaphthalene)Mn(CO)3] with Pyridine in the Presence of Halogenated Solvent: The Role of Ring-Slippage in [(1-H-Hydronaphthalene)Mn(CO)3]

“…It has been reported , that the reaction of [Mn(CO) 5 CH 2 Cl] with PPh 3 in CH 3 CN at room temperature gave [Mn(CO) 3 (PPh 3 ) 2 Cl]. This suggests [Mn(CO) 3 (py) 2 CH 2 Cl] as a plausible intermediate in eq 1.…”

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

“…476 This procedure has also been used to make heterometallic u-ketene complexes with R = CH 2 Fe(CO) 2 Cp from [Fe(CH 2 COCl)(CO) 2 Cp], and the heterometallic complex [Mo {COC 5 H 4 Mn(CO) 3 } (CO) 3 Cp]. 4 With succinoyl or glutarovl chloride, cyclization occurs to give [M{C=CH(CH 2 ) w COO}(CO) 3 472 The reaction of the alkyl complexes [MR(CO) 3 399 ' 400 The latter reaction can be encouraged for other nucleophiles by adding T1BF 4 .…”