Iron carbene complexes. Part 3. Aminolysis of di-iron alkoxycarbene complexes with ammonia and dimethylamine. X-Ray crystal structure of [Fe2(µ-SPh)2(CO)5{C(NMe2)Ph}]

Abstract

Reaction of the mercapto-bridged di-iron carbene complexes [(OC)₃Fe(µ-SPh)₂Fe(CO)₂{C(OEt)Ph}] and [(OC)₃Fe{µ-S(CH₂)₃S}Fe(CO)₂{C(OEt)Bu}] with ammonia and dimethylamine afforded the aminocarbene complexes, [(OC)₃Fe(µ-SPh)₂Fe(CO)₂{C(NR⁴R⁵)Ph}](R⁴,R⁵= H or Me) and [(OC)₃Fe{µ-S(CH₂)₃S}Fe(CO)₂{C(NR⁴R⁵)Bu}](R⁴,R⁵= H or Me). Competitive to the aminolysis reaction is substitution of the carbene ligand by an amine. The structure of [(OC)₃Fe(µ-SPh)₂-Fe(CO)₂{C(NMe₂)Ph}] was confirmed by X-ray crystallography. The crystals are monoclinic, space group P2₁/n with a= 9.987(3), b= 18.955(5), c= 14.557(3)Å, β= 107.74(2)°, and Z= 4. The carbene ligand is in the trans position to the iron–iron bond and the phenyl groups of the bridging sulphur atoms are in an anti orientation.