67588-74-3Relevant academic research and scientific papers
Reactions of (1-3-η-vinylcarbene)tricarbonyliron complexes with carbon monoxide or tertiary phosphines. Insertion of carbon monoxide into a carbon-metal double bond and reactivities of the formed tricarbonyl(η3:η1-allylacyl)irons
Mitsudo, Take-Aki,Watanabe, Hiroyoshi,Sasaki, Teruhiko,Takegami, Yoshinobu,Watanabe, Yoshihisa,Kafuku, Koumei,Nakatsu, Kazumi
, p. 368 - 378 (2008/10/08)
A (η3-vinylcarbene)iron complex, tricarbonyl(1-3-η-1-methoxy-2-(methoxycarbonyl)prop-2-en-1-ylidene)iron (3a), reacts with carbon monoxide (1 atm) or tertiary phosphines (L) at 30-35°C to give Fe(η3:η1-allylacyl)(CO)2L (6, L = CO; 7, L = PPh3; 8, L = PPh2Me; 9, L = PPhMe2) in good to excellent yields; the insertion of a carbon monoxide into the carbene-iron bond readily occurs. Complex 7 crystallizes in space group P21/c with a = 13.926 (2) A?, b = 10.227 (2) A?, c = 35.835 (7) A?, β = 101.81 (2)°, and Z = 8. Pertinent bond distances are C(2)-Fe = 1.899 (7) A?, C(2)-C(3) = 1.484 (11) A?, C(3)-C(4) = 1.403 (10) A?, and C(4)-C(5) = 1.416 (11) A?. These data show that for the description of 7, (η3:η1-allylacyl)tricarbonyliron, is preferable to (η4-vinylketene)tricarbonyliron. Complex 3a reacts with 2 mol equiv of PPhMe2 to give a ferracyclopent-2-en-5-one derivative, 12, in 19% yield. Fe(η3:η1-allylacyl)(CO)2L (8, L = PPh2Me; 9, L = PPhMe2) further reacts with carbon monoxide, PPh2Me, or PPhMe2 to give a ferracyclopent-2-en-5-one derivatives (10, L = L′ = PPh2Me; 11, L = PPhMe2 L′ = CO; 12, L = L′ = PPhMe2). Complex 11 crystallizes in space group P21/n with a = 13.393 (4) A?, b = 16.906 (3) A?, c = 8.774 (2) A?, β = 93.10 (2)°, and Z = 4. Tricarbonyl(1-3-η-1-methoxy-2,3-bis(methoxycarbonyl)prop-2-en-1-ylidene)iron (3b) reacts with carbon monoxide to give tricarbonyl(3-6-η-4-(methoxycarbonyl)-5,6-dimethoxy-2-pyrone)iron (13). Complex 13 belongs to the orthorhombic space group Pbca with a = 13.104 (1) A?, b = 19.646 (2) A?, c = 11.346 (2) A?, and Z = 8. Complex 3b reacts with PPh3 at 50°C to afford the phosphine-substituted η3-vinylcarbene complex 19. Complex 3b reacts with PPh2Me or PPhMe2 to give the corresponding Fe(η3:η1-allylacyl)(CO)2L (14 and 15) which further react with carbon monoxide or PPhMe2 to give ferracyclopent-3-en-2-ones (16, 17, and 18).
