Abstract
The use of the ligands, diethynyldiphenylsilane and 1,3-diethynyltetramethyldisiloxane, in the synthesis of Group 8 metal σ-acetylide mononuclear complexes is demonstrated. New complexes trans-[(dppm) 2ClMCCSi(Ph) 2CCH] (M=Ru 1; Os 2) and trans-[(dppm) 2ClMCCSi(Me) 2–O–Si(Me) 2CCH] (M=Ru, 3; Os, 4) featuring different silyl units were prepared from a mixture of cis-[M(dppm) 2Cl 2] and HCCSi(Ph) 2CCH or HCCSi(Me) 2–O–Si(Me) 2CCH in the presence of NaPF 6 followed by deprotonation with 1,8-diazabicyclo[5.4.0]undec-7-ene. All the new complexes have been fully characterized by FTIR and NMR spectroscopies and fast atom bombardment mass spectrometry. Single-crystal X-ray structures of 1 and 2 confirm that the two diphosphines adopt a trans geometry at the metal centre and one of the terminal ethynyl groups remains intact. Complexes 1– 4 show reversible redox chemistry and their half-wave potentials due to the metal centres are less anodic than those for the starting precursors cis-[M(dppm) 2Cl 2] (M=Ru, Os).
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