The 7-coordinate technetium(III) and rhenium(III) monocapped tris(dioxime) complexes [MX(dioxime) 3 BR] have been prepared in which the seventh ligand, X, is thiocyanate or hydroxide (M ) Tc, Re; R ) Me, Et). Both the N-and S-bound thiocyanate linkage isomers are produced during the syntheses, however, the S-bound complex isomerizes to the N-bound analogue. The synthetic routes employed allowed isolation of sufficient quantities of the technetium and rhenium S-bound isomers to be identified; however, full characterization was not possible. The linkage isomerization reaction of TcSCN(CDOH) 2 (CDO)BMe to TcNCS(CDOH) 2 (CDO)BMe was monitored in dichloromethane by UV-visible spectrophotometry, with four isosbestic points observed, consistent with the formation of a single product. The N-bound isomers for both Tc and Re, and the S-bound isomer of Re were characterized by single-crystal X-ray diffraction analysis. The two N-bound complexes were found to be isostructural. TcNCS(CDOH) 2 (CDO)BMe crystallized in the orthorhombic space group P2 1 2 1 2 1 with a ) 15.814-(2) Å, b ) 17.855(3) Å, c ) 17.997(5) Å, Z ) 8, R ) 0.054, and R W ) 0.057. ReNCS(CDOH) 2 (CDO)BMe crystallized in the orthorhombic space group P2 1 2 1 2 1 with a ) 15.795(1) Å, b ) 17.843(2) Å, c ) 18.014(3) Å, Z ) 8, R ) 0.054, and R W ) 0.073. In both cases two independent molecules per unit cell were observed. ReSCN(CDOH) 2 (CDO)BMe crystallized in the monoclinic space group P2 1 /c with a ) 10.0866(6) Å, b ) 26.301-(2) Å, c ) 12.4592(7) Å, β ) 100.5(1) deg, Z ) 4, R ) 0.100, and R W ) 0.141.