The Re(II) nitrosyl complex [ReCl 2(OMe)(NO)(PPh 3)2] reacts with excess 2,6-Pr 2 iC 6H 3S −(DIPT −) in methanol to give the Re(III) complex [Re(DIPT) 4(NO)] ( I) whereas thiophenolate gives a thiolatobridged Re(II) dimer. Crystal data for( I): crystallizes in the orthorhombic space group Pbca, a = 13.218(6) Å, b = 19.534(9) Å, c = 38.115(13) Å, V = 9841.3(6) Å 3 to give D calc = 1.35 g cm −3 for Z = 8. Structure solution and refinement are based on 3047 reflections with I o>3σ| I o| and yielded a final R value of 0.064. The overall geometry about Re is trigonal bipyramidal with an apical NO group with a nearly linear ReNO system (ReNO, 173.6(14)°). The polymeric species ‘{Mo(NO)(NH 2O)} n’ reacts with excess 2,4,6-Pr 3 iC 6H 2S −(TIPT − to give[Mo(TIPT) 3(NH 3)(NO)]·C 5H 12 ( II) (C 5H 12 = n-pentane) whereas thiophenolate anion gives [Mo(SPh) 4(NO)] −. Crystal data for ( II): space group P2 1/ n with a = 10.477(3) Å, b = 26.359(5) Å, c = 20.124(4) Å, β = 87.21(1)°, with V = 5550.9(12) Å 3 to give D calc = 1.05 g cm −3 for Z = 4. Structure refinement was based on 1040 reflections with I o>3σ| I o| and yielded a final R value of 0.079. The geometry about Mo is again trigonal bipyramidal with apical NO and NH 3 groups and again an essentially linear MoNO system (MNO = 174.2(3)°).