AbstractTwo potentially tripodal ligands, tris(1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)phosphine oxide (OP(1,2,3Tz1−Ph)3) and tris(1‐benzyl‐1H‐1,2,3‐triazol‐4‐yl)phosphine oxide (OP(1,2,3Tz1−benz)3), were used in reactions with [Re(CO)5Br] and (NEt4)2[Tc(CO)3Cl3]. While the formation of rhenium complexes with bidentate and tridentate coordinated phosphine oxides was observed, for technetium only cationic complexes with tripodal coordinated OP(1,2,3Tz1−R) ligands were isolated. The products have been characterized spectroscopically and by single crystal X‐ray diffraction.
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