SHOP-type nickel complexes with alkyl substituents on phosphorus, synthesis and catalytic ethylene oligomerization.

The beta-keto phosphorus ylides (n-Bu)3P=CHC(O)Ph 6, (t-Bu)2PhP=CHC(O)Ph 7, (t-Bu)Ph2P=CHC(O)Ph 8, (n-Bu)2PhP=CHC(O)Ph 9, (n-Bu)Ph2P=CHC(O)Ph 10, Me2PhP=CHC(O)Ph 11 and Ph3P=CHC(O)(o-OMe-C6H4) 12 have been synthesized in 80-96% yields. The Ni(II) complexes [NiPh{Ph2PCH...C(...O)(o-OMeC6H4)}(PPh3)] 13, [NiPh{Ph(t-Bu)PCHC(O)Ph}(PPh3)] 15, [NiPh{(n-Bu)2PCH...C(...O)Ph}(PPh3)] 16 and [NiPh{Ph(n-Bu)PCH...C(...O)Ph}(PPh3)] 17 have been prepared by reaction of equimolar amounts of [Ni(COD)2] and PPh3 with the beta-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 alpha to phosphorus and the ether function. The complexes [NiPh{Ph2PCHC(O)Ph}(Py)] 18, [NiPh{Ph(t-Bu)PCHC(O)Ph}(Py)] 19, [NiPh{(n-Bu)2PCH...C(...O)Ph}(Py)] 20, [NiPh{Ph(n-Bu)PCH...C(...O)Ph}(Py)] 21 and [NiPh{Me2PCH...C(...O)Ph}(Py)] 22 have been isolated from the reactions of [Ni(COD)2] and an excess of pyridine with the -keto phosphorus ylides Ph3PCH=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 12700 mol C2H4 (mol Ni)-1 under 30 bar ethylene. When the beta-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.