Reactions between [Mn(CO)5Br] and dpkbh in low boiling solvents in air gave fac-[MnI(CO)3(κ2-Npy,Nim-dpkbh)Br]·H2O, [MnIIBr2(κ3-Npy,Nim,O-dpkbh)], and [MnII(κ3-Npy,Nim,O-dpkbh-H)2]·0.5H2O (Nim = imine nitrogen and Npy = pyridyl nitrogen). Crystallization of fac-[MnI(CO)3(κ2-Npy,Nim-dpkbh)Br]·H2O from dmso or CH3CN produced dark red crystals of [MnII(κ3-Npy,Nim,O-dpkbh-H)2]·nX (X = dmso, n = 1 and X = H2O, n = 0.22). This is in contrast to the reaction of [Re(CO)5Cl] with dpkbh in refluxing toluene to form fac-[ReI(CO)3(κ2-,Npy,Npy-dpkbh)Cl] which can be crystallized from CH3CN, dmso or dmf to form fac-[ReI(CO)3(κ2-,Npy,Npy-dpkbh)Cl]·nX (X = CH3CN, n = 0 and solvate = dmso or dmf, n = 1). Infrared spectral measurements are consistent with keto coordination of dpkbh to Mn(I) in fac-[MnI(CO)3(κ2-Npy,Nim-dpkbh)Br]·H2O and Mn(II) in [MnIIBr2(κ3-Npy,Nim,O-dpkbh)] plus enol coordination of the amide-deprotonated dpkbh, to the Mn(II) center in [MnII(κ3-Npy,Nim,O-dpkbh-H)2]·0.5H2O. Electronic absorption spectral measurements in non-aqueous solvents indicate sensitivity of fac-[MnI(CO)3(κ2-Npy,Nim-dpkbh)Br]·H2O and [MnII(κ3-Npy,Nim,O-dpkbh-H)2]·0.5H2O to changes in their outer-shell environments. X-ray crystallographic analyses elucidated the identities of [MnIIBr2(κ3-Npy,Nim,O-dpkbh)] and [MnII(κ3-Npy,Nim,O-dpkbh-H)2]·nX and divulged weaker coordination of [dpkbh] to Mn(II) in [MnIIBr2(κ3-Npy,Nim,O-dpkbh)] and stronger coordination of [dpkbh-H]− to Mn(II) in [MnII(κ3-Npy,Nim,O-dpkbh-H)2]·0.22H2O. Low-temperature X-ray structural analyses were employed to account for the disorder in the structure of [MnII(κ3-Npy,Nim,O-dpkbh-H)2] and the short NH bond distance observed in the structure of [MnIIBr2(κ3-Npy,Nim,O-dpkbh)]. A PLATON Squeeze treatment was invoked to account for the fractional occupancy of lattice water in the structure of [MnII(κ3-Npy,Nim,O-dpkbh-H)2].