2012
DOI: 10.2174/2211544711201030149
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Mechanism of Ethylene Oligomerization by the Catalytic System Ni(COD)2 / BF3·OEt2 Modified with Tertiary Phosphines

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Cited by 3 publications
(5 citation statements)
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“…[54,55] The X-ray structure of 4[SbF 6 ] ( Figure 2) revealed that the gold center adopts an essentially linear coordination geometry with a C (carbene) -Au-(-C≡C-centroid ) angle of 176.7°. The Au-C(carbene) and Au-(-C≡C-centroid ) distances are 2.012 (4) 6 ], they were also synthesized via independent routes using authentic free alkenes bicyclo [3.3.0]oct-1(5)-ene (2) [56,57] and cis-bicyclo-[3.3.0]oct-2-ene (3) [58] (prepared following literature procedures), and (IPr)AuSbF 6 6 ] are rotated by about 79°(average) relative to the carbene Au(N-C-N) planes whereas in 6[SbF 6 ], this angle is about 74°. The structurally authenticated alkenes adducts of (IPr)Au + show a range of such inter-planar angles from essentially coplanar to nearly perpendicular suggesting that the relative alkene orientation is determined largely by steric factors, [37] presumably arising from interaction with methyl hydrogens on the IPr ligand.…”
Section: Resultsmentioning
confidence: 99%
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“…[54,55] The X-ray structure of 4[SbF 6 ] ( Figure 2) revealed that the gold center adopts an essentially linear coordination geometry with a C (carbene) -Au-(-C≡C-centroid ) angle of 176.7°. The Au-C(carbene) and Au-(-C≡C-centroid ) distances are 2.012 (4) 6 ], they were also synthesized via independent routes using authentic free alkenes bicyclo [3.3.0]oct-1(5)-ene (2) [56,57] and cis-bicyclo-[3.3.0]oct-2-ene (3) [58] (prepared following literature procedures), and (IPr)AuSbF 6 6 ] are rotated by about 79°(average) relative to the carbene Au(N-C-N) planes whereas in 6[SbF 6 ], this angle is about 74°. The structurally authenticated alkenes adducts of (IPr)Au + show a range of such inter-planar angles from essentially coplanar to nearly perpendicular suggesting that the relative alkene orientation is determined largely by steric factors, [37] presumably arising from interaction with methyl hydrogens on the IPr ligand.…”
Section: Resultsmentioning
confidence: 99%
“…[64] Ni(COD) 2 /BF 3 ·OEt 2 mediated conversion of 1,5-cyclooctadiene to 3 has also been reported. [58] Base mediated routes from 1,5-or 1,3-cyclooctadiene to 3 are available as well. [65] Since one could speculate pathways to ring non-contracted olefins like 1,3-cyclooctadiene and 1,2-cyclooctadiene (an allene) via C-H insertions to 7 (and G rel values for cyclooctyne, 1,3-cyclooctadiene and 1,2-cyclooctadiene are 35.4, 13.6, and 29.8 kcal/mol), we tested the chemistry of 1,3-or 1,5-cyclooctadiene using either gold catalyst or strong acid (100 or 120°C in CHCl 3 ).…”
Section: Resultsmentioning
confidence: 99%
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“…Additionally, alcohols are presented by Saraev et al as promoters of such Ni(0) systems, making possible the generation of an active Ni­(II) hydride or a coordinatively unsaturated cationic Ni­(I) species, described as being ten-times more active catalysts than the Ni­(II) hydride . On the basis of a related system, Kraikivskii et al proposed that when [Ni­(cod) 2 ] is reacted with BF 3 .Et 2 O, ethylene can be dimerized with a Ni­(I)/Ni­(III) metallacyclic mechanism . Schmidt et al.…”
Section: Active Sites and Mechanism(s)mentioning
confidence: 99%
“…Kraikivskii et al proposed that when [Ni(cod) 2 ] is reacted with BF 3 .Et 2 O, ethylene can be dimerized with a Ni(I)/Ni(III) metallacyclic mechanism 428. Schmidt et al focused on the same [Ni(PPh 3 ) 4 ] -BF 3 .Et 2 O system, but he postulated the presence of a Brønsted acid impurity that could form the catalytically active Ni(II) hydride species 429.…”
mentioning
confidence: 99%