Synthesis and Coordination Chemistry of <i>N,N</i>-Diallylbispidine
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The synthesis of 3,7-diallyl-3,7-diazabicyclo[3.3.1]nonane (C7H12N2allyl2, 3) has been revisited, and several hitherto undetected byproducts have been identified. Pure 3 and these byproducts were isolated by both prep-GC and column chromatography. Monoprotonated 3 in the form of the PF6 salt [(C7H13N2allyl2]PF6 (9) and the addition complexes of 3 to Ni(acac)2 and CuI, (C7H12N2allyl2)Ni(acac)2 (10) and {(C7H12N2allyl2)Cu(μ-I)}2 (11), have been prepared. From the reactions of {(η3-C3H5)M(μ-X)}2 (M = Ni, Pd, Pt; X = Cl, Br) with 3 and TlPF6 the complexes [(C7H12N2allyl2)M(η3-C3H5)]PF6 (M = Ni (12a), Pd (12b), Pt (12c)) were obtained. Compounds 9–11 and 12b were characterized by X-ray crystallography. The reaction of (1,5-hexadiene)PtCl2 with 3 gave, after HCl elimination, monomeric {C7H12N2(C3H5)CHCHCH2}PtCl (13a), and the presence of MeOH afforded {C7H12N2(C3H5)CH2CH(OMe)CH2}PtCl (13b), both compounds featuring novel anionic tridentate ligands. Furthermore, chiral N,N′-bis((R)-1-phenylethyl)-1,7-octadiene-(S,S)-4,5-diamine (15) reacts with CuI to give [{(C3H5)2C2H4N2(CHMePh)2}Cu(μ-I)]2 (16). The unbound N-allyl functions on the ligands in the product complexes allow for immobilization of the transition metal complexes on polyester fibers.
