The syntheses of [Mn 2 (CO) 1 0 - x (SbPh 3 ) x ] (x=1 or 2), [Re 2 (CO) 9 (SbPh 3 )], [Mn(CO) 5 (SbPh 3 )][CF 3 SO 3 ], [M(CO) 4 Cl(SbPh 3 )], fac-[M(CO) 3 Cl(SbPh 3 ) 2 ] (M=Mn or Re) and mer,trans-[Mn(CO) 3 Cl(SbPh 3 ) 2 ] are reported. The complexes have been characterised by chemical analysis, IR and multinuclear NMR ( 1 H, 1 3 C{ 1 H} and 5 5 Mn) spectroscopies, and FAB mass spectrometry. The crystal structure of [Mn 2 (CO) 9 (SbPh 3 )] established the axial position of the SbPh 3 ligand (Mn-Sb 2.525(1), Mn-Mn 2.909(1) 9) and that of [Mn(CO) 5 (SbPh 3 )][CF 3 SO 3 ] confirmed the cation structure (Mn-Sb 2.596(3) 9). The crystal structure of fac-[Re(CO) 3 Cl(SbPh 3 ) 2 ] establishes the stereochemistry (Re-Sb 2.726(1), 2.729(2) 9). Differences in the products/isomers produced in reactions of [M 2 (CO) 1 0 ] and [M(CO) 5 Cl] with SbPh 3 and with the corresponding PR 3 and AsR 3 ligands are identified and discussed.