Syntheses, Characterization, and Crystal Structures of Two Trans Six‐Coordinate Germanium(IV) Complexes of H2tmtaa (5,14‐Dihydro‐6,8,15,17‐tetramethyldibenzo[b,i][1,4,8,11]‐tetraazacyclotetradecine)

Abstract The reaction of Ge(tmtaa)Cl2 [5,14‐dihydro‐6,8,15,17‐tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine (H2tmtaa)] and sodium cyanate or sodium acetate under mild conditions results in mononuclear six‐coordinate tmtaa Ge(IV) complexes, Ge(tmtaa)X2 [X=NCO, (1); X=OCOCH3, (2)], containing Ge–N or Ge–O bonds, respectively. The complexes, (1) and (2), have been characterized by IR spectra, UV spectra, mass spectra, NMR spectra, and elemental analyses, as well as DSC measurements. X‐ray crystal structures of (1) and (2) reveal that the tmtaa ligand of the complexes retains the characteristic saddle‐shaped configuration of H2tmtaa and the complexes have adopted six‐coordinate geometries in which two substituents are in trans positions.