Synthesis and reactivity of tantalum alkylidene complexes containing the C,N,N'-chelating aryldiamine ligand [C6H4(CH2N(Me)CH2CH2NMe2)-2](-) (CNN). X-ray structures of [TaCl2(=CH-t-Bu)(CNN)], [Ta{(CH2)(3)-1,3}(CNN)(O-t-Bu)(2)], and [Ta(CNN)(O-t-Bu)(2)(H2C=CH2)]

被引:36
作者
Rietveld, MHP
Teunissen, W
Hagen, H
vandeWater, L
Grove, DM
vanderSchaaf, PA
Muhlebach, A
Kooijman, H
Smeets, WJJ
Veldman, N
Spek, AL
vanKoten, G
机构
[1] UNIV UTRECHT,DEBYE RES INST,DEPT MET MEDIATED SYNTH,NL-3584 CH UTRECHT,NETHERLANDS
[2] CIBA GEIGY LTD,MAT RES,CH-1723 MARLY,SWITZERLAND
[3] UNIV UTRECHT,DEPT CRYSTAL & STRUCT CHEM,BIJVOET CTR BIOMOL RES,NL-3584 CH UTRECHT,NETHERLANDS
关键词
D O I
10.1021/om9606799
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The potentially C,N,N'-chelating anionic aryldiamine ligand [C6H4(CH2N(Me)CH2CH2-nMe(2))-2](-) (CNN) has been employed in the preparation of six-coordinate Ta(V) alkylidene complexes. The new dichloro alkylidene complex [TaCl2(=CH-t-Bu)(CNN)], 2, prepared from [TaCl3(=CH-t-Bu)(THF)(2)] and [Li(CNN)](2), 1, has been obtained as a mixture of three diastereoisomers (2a-c) in 51% yield. The molecular structure of the major isomer 2a, determined by X-ray methods, shows this to be a tetragonal bipyramidal complex in which the metal coordination sphere is comprised of the C,N,N' facially bonded CNN, two cis-positioned chlorides in the equatorial plane, and a neopentylidene group and the NMe2 nitrogen donor mutually trans-positioned at the apices. The dialkoxide complexes [Ta(=CHR)(CNN)(o-t-Bu)(2)] (R = t-Bu (3a), CMe2Ph(3b)) have been obtained by transmetallation of [TaCl(=CHR)(O-t-Bu)(2)(PMe3)] with 1, The neopentylidene complex 3a was isolated as an analytically pure orange solid in 47% yield, whereas the neophylidene complex 3b was isolated as an orange oil of +/-90% purity. Complex 3b reacts in pentane with ethene at room temperature to afford the tantalacyclobutane complex [Ta{(CH2)(3)-1,3}(CNN)(O-t-Bu)(2)], 4, which was isolated as a white solid in 81% yield, An X-ray diffraction study of4 shows it to be a heptacoordinate pentagonal bipyramidal tantalum species in which two mutually trans alkoxide groups are in the apical positions; the meridional ligation is comprised of the C,N,N'-coordination of CNN and the sigma-bonded carbon atoms of the metallacyle. Reaction of 3b in hexane at 69 degrees C with ethene gives a mixture of the new tantalum alkene complex [Ta(CNN)(O-t-Bu)(2)(H2C=CH2)], 5, and 4 in a 5:2 ratio. Complex 5 can be isolated from this mixture as a yellow solid by recrystallization from diethyl ether at -30 degrees C. The X-ray molecular structure of 5 shows it to be a pentagonal bipyramidal complex in which the array of atoms directly bonded Do tantalum is like that in 4. However, in 5, the meridional ligation is comprised of the C,N,N'-coordination of CNN and the two C atoms of the ethene molecule. Complexes 3b and 4 initiate ring-opening metathesis polymerization with strained cyclic olefins; dicyclopentadiene produces cross-linked polymers, whereas norbornene produces polycyclopentamers with approximately 90% trans-vinylene bonds. In contrast, none of the isomers of alkylidene complex 2 show any reactivity toward either ethene or norbornene.
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页码:1674 / 1684
页数:11
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