TY - JOUR
T1 - Oligomerization and cross-oligomerization of terminal alkynes catalyzed by organoactinide complexes
AU - Haskel, Ariel
AU - Straub, Thomas
AU - Dash, Aswini K.
AU - Eisen, Moris S.
PY - 1999/4/7
Y1 - 1999/4/7
N2 - Various organoactinides of the type Cp*2An(C≡CR)2 (Cp* = C5Me5; An = Th, U) have been synthesized from the corresponding Cp*2AnMe2 complexes by addition of an equimolar amount or an excess of the corresponding terminal alkyne. Attempts to trap the mono(acetylide) complexes Cp*2An(C≡CR)(Me) were successful for only the transient species Cp*2U(C≡C(i-Pr))(Me). The bis(acetylide) complexes are active catalysts for the linear oligomerization of terminal alkynes HC≡CR. The regioselectivity and the extent of oligomerization depend strongly on the alkyne substituent R, whereas the catalytic reactivities are similar for both organoactinides. Reaction with tert-butylacetylene regioselectively yields the 2,4-disubstituted 1-butene-3-yne dimer, whereas (trimethylsilyl)acetylene is regioselectively trimerized to (E,E)-1,4,6-tris(trimethylsilyl)-1,3- hexadiene-5-yne, with small amounts (3-5%) of the corresponding 2,4- disubstituted 1-butene-3-yne dimer. Oligomerization with less bulky alkyl- and aryl-substituted alkynes produces a mixture of oligomers. Cross- oligomerizations reactions induce the formation of specific cross dimers and trimers. Mechanistic studies on the selective trimerization of HC≡CSiMe3 show that the first step in the catalytic cycle is the C≡C bond insertion of the terminal alkyne into the actinide-acetylide bond. The kinetic rate law is first order in organoactinide and in alkyne, with ΔH((+)) = 11.1 (3) kcal mol-1 and ΔS((+)) = - 45.2(6) eu. The turnover-limiting step is the release of the organic oligomer from the alkenyl-actinide complex. The latter key organometallic intermediate has been characterized by spectroscopic and poisoning studies. A plausible mechanistic scenario is proposed for the oligomerization of terminal alkynes.
AB - Various organoactinides of the type Cp*2An(C≡CR)2 (Cp* = C5Me5; An = Th, U) have been synthesized from the corresponding Cp*2AnMe2 complexes by addition of an equimolar amount or an excess of the corresponding terminal alkyne. Attempts to trap the mono(acetylide) complexes Cp*2An(C≡CR)(Me) were successful for only the transient species Cp*2U(C≡C(i-Pr))(Me). The bis(acetylide) complexes are active catalysts for the linear oligomerization of terminal alkynes HC≡CR. The regioselectivity and the extent of oligomerization depend strongly on the alkyne substituent R, whereas the catalytic reactivities are similar for both organoactinides. Reaction with tert-butylacetylene regioselectively yields the 2,4-disubstituted 1-butene-3-yne dimer, whereas (trimethylsilyl)acetylene is regioselectively trimerized to (E,E)-1,4,6-tris(trimethylsilyl)-1,3- hexadiene-5-yne, with small amounts (3-5%) of the corresponding 2,4- disubstituted 1-butene-3-yne dimer. Oligomerization with less bulky alkyl- and aryl-substituted alkynes produces a mixture of oligomers. Cross- oligomerizations reactions induce the formation of specific cross dimers and trimers. Mechanistic studies on the selective trimerization of HC≡CSiMe3 show that the first step in the catalytic cycle is the C≡C bond insertion of the terminal alkyne into the actinide-acetylide bond. The kinetic rate law is first order in organoactinide and in alkyne, with ΔH((+)) = 11.1 (3) kcal mol-1 and ΔS((+)) = - 45.2(6) eu. The turnover-limiting step is the release of the organic oligomer from the alkenyl-actinide complex. The latter key organometallic intermediate has been characterized by spectroscopic and poisoning studies. A plausible mechanistic scenario is proposed for the oligomerization of terminal alkynes.
UR - http://www.scopus.com/inward/record.url?scp=0033531631&partnerID=8YFLogxK
U2 - 10.1021/ja9836390
DO - 10.1021/ja9836390
M3 - 文章
AN - SCOPUS:0033531631
SN - 0002-7863
VL - 121
SP - 3014
EP - 3024
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 13
ER -