ISSN:
1434-1948
Keywords:
Nickel(0)
;
Oxidation
;
Phenols
;
Structure
;
Ion pairs
;
Hydrogen bonds
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Admission of molecular oxygen to a solution containing Ni(PMe3)4 and substituted phenols (ArOH) affords bisphenolatonickel compounds trans-Ni(OAr)2(PMe3)2 [ArOH = 2-chlorophenol (1), 2-bromophenol (2), 2,4,6-trichlorophenol (3)]. In the absence of dioxygen the phenols reversibly protonate the nickel complex to form ionic compounds [NiH(PMe3)4]+ Y- containing hydrogen-bonded anions Y = [H2(2-Cl-C6H4O)3] (4), [H(2-OH-C6H4COO)2] (5). As a side-reaction, formal insertion of nickel to give 2-hydroxyphenylnickel compounds Ni(Ar′)X(PMe3)3 [Ar′ = 2-OH-C6H4; × = Br (6), I (7)], trans-Ni(Ar′)Cl(PMe3)2 [Ar′ = 2-OH-3,5-Cl2-C6H2 (8)] and trans-Ni(OAr)Cl(PMe3)2 [Ar = 2,4,6-Cl3-C6H2 (9)] is observed. An X-ray crystal structure determination of 1 shows a trans square planar arrangement of donor atoms, that of 6shows a distorted square pyramid, while 4 contains tetrahedral nickel cations with a delocalized hydrogen atom and triphenolate anions H2(ArO)3-.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
