Abstract: | The pseudo‐square‐planar complexes Rh(cod)(Hbbtm)]BF4 ( 3 ), Rh(bbte)(cod)]BF4 ( 4 ), Rh(CO)2(Hbbtm)]BF4 ( 5 ), Rh(bbte)(CO)2]BF4 ( 6 ), Rh(bbtm)(cod)] ( 7 ) and Rh(bbtm)(CO)2] ( 8 ) (Hbbtm=bis(benzothiazol‐2‐yl)methane=2,2′‐methylenebisbenzothiazole], bbte=bis(benzothiazol‐2‐yl)ethane=2,2′‐(ethane‐1,2‐diyl)bisbenzothiazole], and cod=cycloocta‐1,5‐diene) were synthesized and characterized. Diastereotopic protons were observed for the protons at the bridge in the 1H‐NMR of 3 and 5 . Twisting of the ethane‐1,2‐diyl bridge in 4 and 6 effects chemical equivalence of the CH2 groups in solution. Unusually large downfield shifts occur on coordination of the deprotonated ligand Hbbtm as the negative charge is delocalized in 7 and 8 . The NMR signals of the cod ligand in 4 could be differentiated. The X‐ray crystal structures of 3, 4 , and 6 are reported. |