Alkylene dithiophosphate derivatives of macrocyclic complexes of Mn(II) having O N2S2 potential donors, of the general formula [M(L){S2P G}2] (where M= Mn(II), O Fe(III), & Co(III); L= Macrocyclic ligands, L1, L2, L3, L4 and L5 where G = (CH3)2 CCH2CH(CH3), CH2C(CH3)2CH2, CH2C(C2H5)2CH2 ,CH(CH3).(CH3)CH and C(CH3)2.(CH3)2C have been synthesized from the reaction of [M(L)Cl2/Cl3] with ammonium alkylene dithiophosphates in 1:2 molar ratios in THF. Fifteen new derivatives (1-15) have been synthesized by the combination of five macrocyclic complexes of 14-20 membered rings with different types of alkylene dithiophosphates. These complexes have been characterized by elemental analysis, molar conductance, molecular weight determinations & various spectroscopic techniques IR, 31P NMR, electronic spectra, EPR, Mössbauer, mass spectra and X-ray powder diffraction. Molecular weight determination and magnetic measurements of these complexes indicate their monomeric nature. Octahedral structures have been proposed for these complexes, on the basis of 31P NMR, electronic spectra and magnetic measurements in which two sulfur atoms and two nitrogen atoms of the macrocyclic ring coordinate to the central metal ion in square–planar geometry and each dithiophosphate moiety occupies the axial positions binding the central metal ion in unidentate manner.