TY - JOUR
T1 - Synthetic Applications of Trialkylaluminum Reagents
T2 - Alkylation and Reduction of Transition-Metal-Complexed π-Hydrocarbon Ligands
AU - Gaudet, Michele V.
AU - Zaworotko, Michael J.
AU - Hanson, Alfred W.
AU - White, Peter S.
PY - 1989/2
Y1 - 1989/2
N2 - Trialkylaluminum compounds (A1R3, R = Me, Et) interact with the organotransition-metal cations [(arene)Mn(CO)3]+(1) and [Co(C5H5)]+ (2) to form “liquid clathrate” phases. Thermal decomposition of these phases results in isolation of a series of neutral cyclohexadienyl, 3a-d, or cyclopentadiene, 4, products which are simple addition products except in the case of 1d (arene - mesitylene), for which, depending upon the reaction conditions, isomeric forms of the novel dimer (C18H24)[Mn(CO)3]2 (5a or 5b) have been isolated. It was found that preformed “liquid clathrates” containing the anions [Al2R6Cl]-(R = Me, Et), which possess a much higher degree of air stability than the corresponding free trialkylaluminum compounds, reacted with 1 and 2 to give the same range of products. The structures of 5a and 5b have been determined crystallographically. 5a: triclinic; P1; a = 8.529 (3) Å, b = 9.189 (2) Å, c = 8.488 (3) Å; α = 104.21 (3)°, β = 118.10 (3)°, γ = 89.43 (3)°, V = 564.4 Å3; Z = 1; p = 1.524 g cm-3; R = 0.041. 5b: monoclinic; P21/c; a = 12.2916 (19) Å, b = 15.8372 (21) Å, c = 12.2308 (13) Å; β = 101.757 (11)°; V = 2331.0 Å3; Z = 4; ρ = 1.477 g cm-3; R = 0.057. The structure of the addition product 3d (R = Me) was also crystallographically determined, and exo addition of the methyl was thereby confirmed. 3d: monoclinic; P21/n; a = 11.956 (1) Å, b = 11.441 (1) Å, c = 10.104 (1) Å; β = 104.28 (1)°; V = 1339.4 Å3; Z = 4; p = 1.360 g cm-3; R = 0.042.
AB - Trialkylaluminum compounds (A1R3, R = Me, Et) interact with the organotransition-metal cations [(arene)Mn(CO)3]+(1) and [Co(C5H5)]+ (2) to form “liquid clathrate” phases. Thermal decomposition of these phases results in isolation of a series of neutral cyclohexadienyl, 3a-d, or cyclopentadiene, 4, products which are simple addition products except in the case of 1d (arene - mesitylene), for which, depending upon the reaction conditions, isomeric forms of the novel dimer (C18H24)[Mn(CO)3]2 (5a or 5b) have been isolated. It was found that preformed “liquid clathrates” containing the anions [Al2R6Cl]-(R = Me, Et), which possess a much higher degree of air stability than the corresponding free trialkylaluminum compounds, reacted with 1 and 2 to give the same range of products. The structures of 5a and 5b have been determined crystallographically. 5a: triclinic; P1; a = 8.529 (3) Å, b = 9.189 (2) Å, c = 8.488 (3) Å; α = 104.21 (3)°, β = 118.10 (3)°, γ = 89.43 (3)°, V = 564.4 Å3; Z = 1; p = 1.524 g cm-3; R = 0.041. 5b: monoclinic; P21/c; a = 12.2916 (19) Å, b = 15.8372 (21) Å, c = 12.2308 (13) Å; β = 101.757 (11)°; V = 2331.0 Å3; Z = 4; ρ = 1.477 g cm-3; R = 0.057. The structure of the addition product 3d (R = Me) was also crystallographically determined, and exo addition of the methyl was thereby confirmed. 3d: monoclinic; P21/n; a = 11.956 (1) Å, b = 11.441 (1) Å, c = 10.104 (1) Å; β = 104.28 (1)°; V = 1339.4 Å3; Z = 4; p = 1.360 g cm-3; R = 0.042.
UR - http://www.scopus.com/inward/record.url?scp=0001222728&partnerID=8YFLogxK
U2 - 10.1021/om00104a004
DO - 10.1021/om00104a004
M3 - Article
AN - SCOPUS:0001222728
SN - 0276-7333
VL - 8
SP - 286
EP - 293
JO - Organometallics
JF - Organometallics
IS - 2
ER -