Two nitrosyl Re(II) complexes formulated as [Ni(bipy)3][Re(NO)Br4(pyz)]2 and [Cu(bipy)2Br][ReNOBr4(pyz)] (pyz = pyrazine, bipy = 2,2′-bipyridine) were synthesized and characterized by single-crystal X-ray diffraction. The pyrazine in [Re(NO)Br4(pyz)]− was not able to act as bridge toward a second metal ion, and the two salts were obtained. Computational studies at the density functional level of theory show that the charge on the nitrogen, which could be available for bridging, is dramatically reduced to less than half, decreasing its capability to bind a second metal ion.