The reactions of trans-[PtCl₄(RCN)₂] (R= Me, Et, CH₂Ph, Ph) with the diamines and the triamine NH₂{spacer}NH₂ (spacer = CH₂CH₂, CH(Me)CH₂, CH₂CH₂CH₂, CH₂CH₂CH₂CH₂, CH₂CH₂NHCH₂CH₂) in a molar ratio 1 : 2 produce trans-[PtCl₄{NH=C(R)NH{spacer}NH₂}₂] (spacer/R = CH₂CH₂/Et 1, CH₂CHMe/Et 2 (a mixture of regioisomers), CH₂CH₂CH₂/Et 3, CH₂CH₂CH₂CH₂/Et 4, CH₂CH₂/Me 5, CH₂CH₂/CH₂Ph 6, CH₂CH₂/Ph 7, CH₂CH₂NHCH₂CH₂/Et 8) with the monodentately coordinated amidine ligands having the pendant NH₂ groups. The complexes have been characterised by C, H, and N elemental analyses, ¹³C CP-MAS NMR and IR spectroscopy, (TOF)-ESI-MS, and [1·H₂](Pic)₂·EtOH also by X-ray diffraction.