Synthese, Strukturen, EPR‐ und NMR‐Untersuchungen von N,N′‐o‐Phenylen‐bis(N″,N″‐dialkyl‐N‴‐benzimidoyl‐thioureato)‐Komplexen des NiII und CuII (alkyl = C2H5, i‐C4H9) sowie des Benzo[b]pyrimido‐[1,6‐d][1,4]diazepin‐12‐ium‐dichlorocuprats(I)

Synthesis, Structures, EPR and NMR Investigations of N,N′‐o‐Phenylen‐bis(N″,N″‐dialkyl‐N‴‐benzimidoyl‐thioureato) Complexes of NiII and CuII (alkyl = C2H5, i‐C4H9) and of Benzo[b]pyrimido‐[1,6‐d][1,4]diazepin‐12‐ium‐dichlorocuprate(I) The synthesis of NiII and CuII complexes of the quadridentate N,N′‐o‐phenylen‐bis(N″,N″‐dialkyl‐N‴‐benzimidoyl‐thiourea) ligands H2L1 (alkyl = C2H5) and H2L2 (alkyl = i‐C4H9) and the crystal structures of CuIIL1 and NiIIL2 are reported. CuIIL1 crystallizes triclinic, P 1 (Z = 2) and NiIIL2 crystallizes orthorhombic, Pbca (Z = 8). CuIIL2 could not be obtained as a pure compound; instead of this benzo[b]pyrimido‐[1,6‐d][1,4]diazepin‐12‐ium‐dichlorocuprate(I) was isolated and characterized by NMR investigations (1H, 13C, APT, H,H COSY, HSQC, HMBC) and by X‐ray diffraction. It crystallizes monoclinic, P21/n with Z = 4. The CuII complexes were studied by EPR; CuIIL1 in liquid and frozen solutions, CuIIL2 in diamagnetically diluted CuII/NiIIL2 powders. The well‐resolved 14N and the 63,65Cu hyperfine couplings were used to analyze the spin‐density distribution in the first coordination sphere.