Zur Reaktivität des Ferriophosphaalkens (Z)-[Cp*(CO)2FeP=C(tBu)NMe2] gegenüber Propiolsäureestern HC≡C-CO2R (R=Me, Et) und Acetylendicarbonsäureestern RO2C-C≡C-CO2R (R=Me, Et, tBu)

Abstract

Inhaltsübersicht. Bei der Umsetzung äquimolarer Mengen an [(Z)-Cp*(CO) 2 FePϭC(tBu)NMe 2 ] (3) mit den Propiolsäureestern HCϵC-CO 2 R 2(a:RϭMe, b:Et) sowie den Acetylendicarbonsäure-estern RO 2 C-CϵC-CO 2 R 1(a:RϭMe, b:Et, c:tBu) bilden sich fünf-gliedrige Metallaheterocyclen On the Reactivity of the Ferriophosphaalkene (Z)-[Cp*(CO) 2 Fe-P‫؍‬C(tBu)NMe 2 ] towards Propiolates HCϵC-CO 2 R (R‫؍‬Me, Et) and Acetylene Dicarboxylates RO 2 C-CϵC-CO 2 R (R‫؍‬Me, Et, tBu).Abstract. The reaction of equimolar amounts of (Z)-[Cp*(CO) 2-FePϭC(tBu)NMe 2 ] 3 and methyl-and ethyl-propiolate (2a, b) or of 3 and dialkyl acetylene dicarboxylates 1a (RϭMe), 1b (Et), 1c(tBu) afforded the five-membered metallaheterocycles [Cp*(CO)F Te-C(ϭO)-C(CO 2 R)ϭCHP UϭC(tBu)NMe 2 ] (4a,b) and [Cp*(CO)F Te-C(ϭO)-C(CO 2 R)ϭC(CO 2 R)-P UϭC(tBu)NMe 2 ] (5a؊c). The mole-1 Einleitung

Nucleophilicity and P–C Bond Formation Reactions of a Terminal Phosphanido Iridium Complex

“…The C23−C37 and C37−C38 bond distances are appropriate for single and double carbon-carbon bonds, respectively ( Figure 7) and comparable to related metallacyclophosphapentenone complexes of iron, molybdenum, or tungsten. 32 In good agreement, the angles around C37 and C38 of the incorporated alkyne fit with that expected for a sp 2 hybridization, reflecting clearly the formation of an olefin as a result of the formal cycloaddition process. Spectroscopic data of complex 8 in solution reflect accurately the structure observed in the solid state.…”

“…All other chemicals are commercially available and were used without further purification. 32;H,4.39;N,6.97. Found: C,52.58;H,4.55;N,6.72; Λ M = 57.9 Ω −1 cm 2 mol −1 (acetone, 5.0x10 −4 M).…”

Ambiphilic Reactivity of a Ruthenaphosphaalkenyl: Synthesis of P-Pyrazolylphosphaalkene Complexes of Ruthenium(0)

“…Investigation of the chemistry of P -metallaphosphaalkenes has included demonstration of their cycloadditions with alkenes, alkynes, and azo and diazo compounds; , additionally, the P δ− C δ+ polarization achieved within C -amino derivatives has been exploited in protonation and alkylation reactions . Significantly, comparable reactivity toward electrophilic species has been demonstrated for 1 , which is devoid of additional π-donor substituents.…”