dppf-like compounds and method of manufacture and use
A method of β-hydride elimination and subsequent 2,1-insertion from a transient nickel(II) acrylate hydride intermediate (Structure I). Also addressed is treatment of (dppe)Ni(CH(CH 3 )CO 2 BAr f 3 ) with a nitrogen containing base to produce a diphosphine nickel(0) η 2 -acryl borate adduct.
1. The composition
where Fc is ferrocene;
where P is phosphorus
where Ph is a phenyl group;
where Ar f is a fluorinated aryl substituent;
where B in BAr f 3 is a boron linked to three fluorinated aryl substituents;
where aryl refers to a functional group or substituent derived from an aromatic ring; and,
where superscript f references a haloginated aryl, phenyl, naphthyl, thienyl, or indolyl.
2. The composition of claim 1 wherein said Ar f 3 is pentafluorophenyl.
3. The composition of claim 1 in the configuration
4. The composition of claim 1 in the configuration
5. The composition of the structure
where Fc is ferrocene;
where P is phosphorus
where R 1 is C 1 -C 12 alkyl, C 3 -C 10 -cycloalkyl which is unsubstituted or may bear a C 1 -C 4 -alkyl group, or aryl which is unsubstituted or may bear one or two substituents selected from chlorine, C 1 -C 8 -alkyl and C 1 -C 8 -alkoxy;
where Ar f is a fluorinated aryl substituent;
where B in BAr f 3 is a boron linked to three fluorinated aryl substituents;
where aryl refers to a functional group or substituent derived from an aromatic ring; and,
where superscript f references a haloginated aryl, phenyl, naphthyl, thienyl, or indolyl.
6. A method of manufacturing producing structure I, Ia or Ib by the steps of reacting a Lewis acid (LA) with (L)nickelalactone and BAr f 3 ;
where L is selected from the group comprising 1,1′-bis(diphenylphosphino)ferrocene (dppf), butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-undecylamine, tri-n-dodecylamine, tri-n-tridecylamine, tri-n-tetradecylamine, tri-n-pentadecylamine, tri-n-hexadecylamine, tri(2-ethylhexyl)amine, dimethyldecylamine, dimethyldodecylamine, dimethyltetradecylamine, ethyldi(2-propyl)amine, dioctylmethylamine, dihexylmethylamine, tricyclopentylamine, tricyclohexylamine, tricycloheptylamine, tricyclooctylamine, and the derivatives thereof substituted by one or more methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl or 2-methyl-2-propyl groups; dimethylcyclohexylamine, methyldicyclohexylamine, diethylcyclohexylamine, ethyldicyclohexylamine, dimethylcyclopentylamine, methyldicyclopentylamine, triphenylamine, methyldiphenylamine, ethyldiphenylamine, propyldiphenylamine, butyldiphenylamine, 2-ethylhexyldiphenylamine, dimethylphenylamine, diethylphenylamine, dipropylphenylamine, dibutylphenylamine, bis-(2-ethylhexyl)phenylamine, tribenzylamine, methyldibenzylamine, ethyldibenzylamine and the derivatives thereof substituted by one or more methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl or 2-methyl-2-propyl groups, N—C 1 - to —C 12 -alkylpiperidines, N,N′-di-C 1 - to —C 12 -alkylpiperazines, N—C 1 - to —C 12 -alkylpyrrolidines, N—C 1 - to —C 12 -alkylimidazoles, and the derivatives thereof substituted by one or more methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl or 2-methyl-2-propyl groups, 1,4-diazabicyclo[2.2.2]octane (DABCO) N-methyl-8-azabicyclo[3.2.1]octane (tropane), N-methyl-9-azabicyclo[3.3.1]nonane (granatane), 1-azabicyclo[2.2.2]octane (quinuclidine); and
where LA comprises
BR 1 R 2 R 3 , Al R 1 R 2 R 3 , or LnX 2 where Ln is a lanthanide;
X is a halogen, triflate, or pseudohalide (each X need not be identical), and
the Lewis acid further comprising inorganic cationic salts of sodium, lithium, potassium, cesium, magnesium, calcium, barium, strontium, or transition metal.
7. The composition of claim 5 wherein
where R 1 is selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 1-(2-methyl)propyl, 2-(2-methyl)propyl, 1-pentyl, 1-(2-methyl)pentyl, 1-hexyl, 1-(2-ethyl)hexyl, 1-heptyl, 1-(2-propyl)heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, and 1-dodecyl.
8. The Composition of claim 5 wherein said C 3 -C 10 -cycloalkyl is selected from the group consisting of cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl and norbornyl.
9. The composition of claim 5 wherein said aryl is selected from the group consisting of phenyl, napthyl, tolyl, xylyl, chlorophenyl and anisyl.