Novel heteroleptic magnesium complexes, [Mg(dmamp)(acac)]2 (), [Mg(dmamp)(tmhd)]2 (), [Mg(dmamp)(tfac)]2 (), and [Mg(dmamp)(hfac)]2 (), were successfully synthesized using dmamp and β-diketonate as ligands. The thermogravimetric analyses and volatile studies of the complexes showed that the complexes and display high volatility and thermal stability. The single crystal X-ray study of the complexes reveals that both the complexes and were crystalized in the triclinic space group and as dimers, where magnesium atoms are in the pentacoordinate state with distorted trigonal bipyramidal geometry.