A series of complexes of the type Rh(cyclam)X,+ and Rh(cyclam)XYn+ have been prepared and characterized, where cyclam represents 1,4,8,11-tetraazacyclotetradecane and X and Y represent OH-, H,O, CI-, Br-, I-, Ns-, NCS-, and NOz-. The infrared and electronic spectra are discussed with respect to assignment of the cis and trolls isomers, the linkage isomers, and the Rh-ligand stretching frequencies above 250 cm-'. The thermodynamic tratls effect is related to shifts in the Rh-ligand stretching frequencies. The intensities of the d-d transitions are related to distortion of the octahedral field to support the cis and tram assignments, and compared to show the decrease in bond constraint for propylene linkages in place of ethylene. Steric constraint accounts for the single case of stereoisomerization by cis-Rh(cyclam)12 +.

Die cis‐ und trans‐Rh(III)‐Komplexe werden aus Rh(III)‐chlorid und dem N4‐Liganden (dargestellt aus 1,3‐Dibrom‐propan und 1,9‐Diamino‐3,7‐diazanonan nach einem verbesserten Verfahren, Ausbeute 6%) bzw. durch Austausch der einzähnigen Liganden der entsprechenden Isomeren (I) bzw. (V I) gegen Na‐Salze dargestellt (Elektronen‐, IR‐Spektren, Bindungseigenschaften).