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

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 [{(η4-1,5-C8H12)RhCl}2{μ-1,3-C6H4(CMe2NH2)2}] (3) resulted from the action of 2 on [{(η4-1,5-C8H12)Rh(μ-Cl)}2] in toluene. Combination of 2 with PdCl2 or K2[PdCl4] gave the dipalladium macrocycle trans,trans-[{μ-1,3-C6H4(CMe2NH2)2}2(PdCl2)2] (4) along with cyclometalated [{2,6-C6H3(CMe2NH2)2-κN,κC1,κN′}PdCl] (5). Substitution of PEt3 for the labile chlorido ligand of 5 afforded [{2,6-C6H3(CMe2NH2)2-κN,κC1, κN′}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).

Both N,N-bridged and N ∩ C ∩ N-chelated complexes were obtained by reactions of rhodium and palladium precursors with the meta-phenylene-based ditertiary carbinamine 1,3-C6H4(CMe2NH2)2, for which a straightforward two-step synthesis is reported.Figure optionsDownload as PowerPoint slide