1,3-Bis(alpha-aminoisopropyl)benzene, meta-C6H4(CMe2NH2)(2): An N,N-bridging and N,C,N-cyclometalating ligand

摘要

Saponification of the bis(carbamic acid ester) 1,3-C6H4(CMe2NHCO2Me)(2) (1), made by the addition of methanol to commercial 1,3-C6H4(CMe2NCO)(2), yielded the meta-phenylene-based bis(tertiary carbinamine) 1,3-C6H4(CMe2NH2)(2) (2). Dinuclear [{(eta(4)-1,5-C8H12) RhCl}(2){mu-1,3-C6H4(CMe2NH2)(2)}] (3) resulted from the action of 2 on [{(eta(4)-1,5-C8H12)Rh(mu-Cl)}(2)] in toluene. Combination of 2 with PdCl2 or K-2[PdCl4] gave the dipalladium macrocycle trans, trans-[{mu-1,3-C6H4(CMe2NH2)(2)}(2)(PdCl2)(2)] (4) along with cyclometalated [{2,6-C6H3(CMe2NH2)(2)-kappa N, kappa C-1, kappa N'}PdCl] (5). Substitution of PEt3 for the labile chlorido ligand of 5 afforded [{2,6-C6H3(CMe2NH2)(2)-kappa N,kappa C-1, kappa N'}Pd(PEt3)]Cl (6). The crystal structures of the following compounds were determined: bis(carbamic acid ester) 1, ligand 2 as its bis(trifluoroacetate) salt [1,3-C6H4(CMe2NH3)(2)](O2CCF3)(2), 2. (HAcf)(2), complexes 3 and 6, as well as 1,3-C6H4(CMe2OH)(2) (the diol analogue of 2). (C) 2007 Elsevier B.V. All rights reserved.