TY - JOUR
T1 - C-F Bond activation at Ni(0) and simple reactions of square planar Ni(II) fluoride complexes
AU - Burling, Suzanne
AU - Elliott, Paul I P
AU - Jasim, Naser A.
AU - Lindup, Richard J.
AU - McKenna, Jennifer
AU - Perutz, Robin N.
AU - Archibald, Stephen J.
AU - Whitwood, Adrian C.
PY - 2005/11/21
Y1 - 2005/11/21
N2 - The reaction of Ni(COD)2 (COD = 1,5-cyclooctadiene) with triethylphosphine and pentafluoropyridine in hexane has been shown previously to yield trans-[NiF(2-C5NF4)(PEt3)2] (1a) with a preference for reaction at the 2-position of the heteroaromatic. The corresponding reaction with 2,3,5,6-tetrafluoropyridine was shown to yield trans-[NiF(2-C5NF3H)(PEt3)2] (1b). In this paper, we show that reaction of Ni(COD)2 with triethylphosphine and pentafluoropyridine in THF yields a mixture of 1a and 1b. Competition reactions of Ni(COD)2 with triethylphosphine in the presence of mixtures of heteroaromatics in hexane reveal a kinetic preference of k(pentafluoropyridine) : k(2,3,5,6-tetrafluoropyridine) = 5.4 : 1. Treatment of 1a and 1b with Me3SiN3 affords trans-[Ni(N 3)(2-C5NF4)(PEt3)2] (2a) and trans-[Ni(N3)(2-C5NHF3)(PEt 3)2] (2b), respectively. The complex trans-[Ni(NCO)(2- C5NHF3)(PEt3)2] (3b) is obtained on reaction of 1b with Me3SiNCO and by photolysis of 2b under CO, while trans-[Ni(η1-C≡CPh)(2-C5NF4)(PEt 3)2] (4a) is obtained by reaction of phenylacetylene with 1a. Addition of KCN, KI and NaOAc to complex 1a affords trans-[Ni(X)(2-C 5NF4)(PEt3)2] (5a X = CN, 6a X = I, 7a X = OAc), respectively. The PEt3 groups of complex 1a are readily replaced by addition of 1,2-bis(dicyclohexylphosphino)ethane (dcpe) to produce [NiF(2-C5F4N)(dcpe)] (8a). Addition of dcpe to trans-[Ni(OTf)(2-C5F4N)(PEt3)2] (10a), however, yields the salt [Ni(2-C5F4N)(dcpe) (PEt3)](OTf) (9a) by substitution of only one PEt3 and displacement of the triflate ligand. The structures of 2b, 4a, 7a and 8a were determined by X-ray crystallography. The influence of different ancillary ligands on the bond lengths and angles of square-planar nickel structures with polyfluoropyridyl ligands is analysed.
AB - The reaction of Ni(COD)2 (COD = 1,5-cyclooctadiene) with triethylphosphine and pentafluoropyridine in hexane has been shown previously to yield trans-[NiF(2-C5NF4)(PEt3)2] (1a) with a preference for reaction at the 2-position of the heteroaromatic. The corresponding reaction with 2,3,5,6-tetrafluoropyridine was shown to yield trans-[NiF(2-C5NF3H)(PEt3)2] (1b). In this paper, we show that reaction of Ni(COD)2 with triethylphosphine and pentafluoropyridine in THF yields a mixture of 1a and 1b. Competition reactions of Ni(COD)2 with triethylphosphine in the presence of mixtures of heteroaromatics in hexane reveal a kinetic preference of k(pentafluoropyridine) : k(2,3,5,6-tetrafluoropyridine) = 5.4 : 1. Treatment of 1a and 1b with Me3SiN3 affords trans-[Ni(N 3)(2-C5NF4)(PEt3)2] (2a) and trans-[Ni(N3)(2-C5NHF3)(PEt 3)2] (2b), respectively. The complex trans-[Ni(NCO)(2- C5NHF3)(PEt3)2] (3b) is obtained on reaction of 1b with Me3SiNCO and by photolysis of 2b under CO, while trans-[Ni(η1-C≡CPh)(2-C5NF4)(PEt 3)2] (4a) is obtained by reaction of phenylacetylene with 1a. Addition of KCN, KI and NaOAc to complex 1a affords trans-[Ni(X)(2-C 5NF4)(PEt3)2] (5a X = CN, 6a X = I, 7a X = OAc), respectively. The PEt3 groups of complex 1a are readily replaced by addition of 1,2-bis(dicyclohexylphosphino)ethane (dcpe) to produce [NiF(2-C5F4N)(dcpe)] (8a). Addition of dcpe to trans-[Ni(OTf)(2-C5F4N)(PEt3)2] (10a), however, yields the salt [Ni(2-C5F4N)(dcpe) (PEt3)](OTf) (9a) by substitution of only one PEt3 and displacement of the triflate ligand. The structures of 2b, 4a, 7a and 8a were determined by X-ray crystallography. The influence of different ancillary ligands on the bond lengths and angles of square-planar nickel structures with polyfluoropyridyl ligands is analysed.
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UR - http://pubs.rsc.org/en/journals/journalissues/dt#!recentarticles&adv
U2 - 10.1039/b510052f
DO - 10.1039/b510052f
M3 - Article
AN - SCOPUS:27944450151
SP - 3686
EP - 3695
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 22
ER -