Two structurally characterized manganese [L2Mn(CO)(4)](+)[Mn(CO)(5)](-) (1) and rhenium [L3Re(CO)(3)](+)[ReCO)(5)](-) (2) silyiene complexes were prepared in one pot syntheses by reacting 1 equivalent of Mn-2(CO)(10) with 2 equivalents of stable N-heterocyclic chlorosilylene L {L = PhC(NtBu)(2) SiC1} and 1 equivalent of Re-2(CO)(10) with 3 equivalents of L in toluene at room temperature. Both complexes 1 and 2 were characterized by single-crystal X-ray structural analysis, NMR and IR spectroscopy, EI-MS spectrometry, and elemental analysis.