SHOP-type nickel complexes with alkyl substituents on phosphorus, synthesis and catalyticethylene oligomerization??

Dalton Transactions Pub Date: 2007-12-06 DOI: 10.1039/B713451G

Abstract

The β-keto phosphorus ylides (n-Bu)3P[double bond, length as m-dash]CHC(O)Ph 6, (t-Bu)2PhP[double bond, length as m-dash]CHC(O)Ph 7, (t-Bu)Ph2P[double bond, length as m-dash]CHC(O)Ph 8, (n-Bu)2PhP[double bond, length as m-dash]CHC(O)Ph 9, (n-Bu)Ph2P[double bond, length as m-dash]CHC(O)Ph 10, Me2PhP[double bond, length as m-dash]CHC(O)Ph 11 and Ph3P[double bond, length as m-dash]CHC(O)(o-OMe-C6H4) 12 have been synthesized in 80–96% yields. The Ni(II) complexes [N[upper bond 1 start]iPh{Ph2PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])(o-OMeC6H4)}(PPh3)] 13, [N[upper bond 1 start]iPh{Ph(t-Bu)PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}(PPh3)] 15, [N[upper bond 1 start]iPh{(n-Bu)2PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}(PPh3)] 16 and [N[upper bond 1 start]iPh{Ph(n-Bu)PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}(PPh3)] 17 have been prepared by reaction of equimolar amounts of [Ni(COD)2] and PPh3 with the β-keto phosphorus ylides 12 or 8–10, respectively, and characterized by 1H and 31P{1H} NMR spectroscopy. NMR studies and the crystal structure determination of 13 indicated an interaction between the hydrogen atom of the C–H group α to phosphorus and the ether function. The complexes [N[upper bond 1 start]iPh{Ph2PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}(Py)] 18, [N[upper bond 1 start]iPh{Ph(t-Bu)PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}(Py)] 19, [N[upper bond 1 start]iPh{(n-Bu)2PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}(Py)] 20, [N[upper bond 1 start]iPh{Ph(n-Bu)PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}(Py)] 21 and [N[upper bond 1 start]iPh{Me2PCH[horiz bar, triple dot above]C([horiz bar, triple dot above]O[upper bond 1 end])Ph}(Py)] 22 have been isolated from the reactions of [Ni(COD)2] and an excess of pyridine with the β-keto phosphorus ylides Ph3PCH[double bond, length as m-dash]C(O)Ph 3 or 8–11, respectively, and characterized by 1H and 31P{1H} NMR spectroscopy. Ligands 3, 8, 10 and 12 have been used to prepare in situ oligomerization catalysts by reaction with one equiv. of [Ni(COD)2] and PPh3 under an ethylene pressure of 30 or 60 bar. The catalyst prepared in situ from 12, [Ni(COD)2] and PPh3 was the most active of the series with a TON of 12?700 mol C2H4 (mol Ni)?1 under 30 bar ethylene. When the β-keto phosphorus ylide 8 was reacted in situ with three equiv. of [Ni(COD)2] and one equiv. of PPh3 under 30 bar of ethylene, ethylene polymerization was observed with a TON of 5500 mol C2H4 (mol Ni)?1.

Graphical abstract: SHOP-type nickel complexes with alkyl substituents on phosphorus, synthesis and catalytic ethylene oligomerization
Recommended Literature