Synthesis and Coordination Chemistry of N,N-Diallylbispidine

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)­CHCHCH2}­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.