Kinetics of nucleophilic attack on co-ordinated organic moieties. Part 7. Mechanisms of addition of tertiary phosphines and phosphites to tricarbonyl(dienyl)iron cations

Nucleophilic addition to coordinated cyclic .pi.-hydrocarbons: mechanistic and synthetic studies

“…The functionalization of arenes by such useful nucleophiles should prove to be a valuable procedure, particularly since strong directive effects are seen. For example, Grignard reagents are directed exclusively meta to the OMe~in Mn(CO)3(anisole)+.105 Somewhat weaker directive effects are found with addition of hydride or an organolithium reagent.106 Another interesting aspect of our work is the observation that refluxing 23 in acidified CH3CN frees the functionalized arene without destroying the Mn(CO)3+ moiety, which can be isolated as [(CH3CN)3Mn(CO)3]PF6 and recycled to give starting material 22. The mechanism of this reaction in CH3CN probably involves endo hydride migration to the metal, reaction with H+ to give H2, and then known14 solvolysis to give the products.…”

Nucleophilie‐ und Elektrophilieskalen als Ordnungsprinzipien polarer organischer und metallorganischer Reaktionen

“…In den Arbeitskreisen von Ritehie [20] und Kane-Maguire 1211 wur den meist Stopped-flow-Techniken (UV/VIS) eingesetzt, mit de nen auch schnellere Reaktionen untersucht werden können. Bei Carbonylkomplexen wurde auch die IR-Spektroskopie verwen det [21] . und Phosphanen [14] wurde gezeigt, daß die Reaktionsgeschwindigkeit durch das Lösungsmittel kaum beeinflußt wird (Tabelle 1), da im ge schwindigkeitsbestimmenden Schritt weder Ladungen "erzeugt" noch ,,vernichtet" werden.…”

Approaches to enantioselective syntheses using tricarbonyl(diene)iron complexes

“…The two samples of complex (2) recovered exhibit equal but opposite optical rotations : (S)( +) isomer [generated from (lla)], a(589 nm, 20 "C, 6 g 100 C M -~ in MeCN, 1 dm) = +120"; ( R ) ( -) isomer [generated from (llb)], a = -116".…”