Sulfur difluoride and sulfur monofluoride as ligands in iron carbonyl chemistry

Abstract

Density functional theory predicts Fe2(SF2)2(CO)n (n = 8, 7) structures with bridging SF2 groups.

Reactivity of Binary and Ternary Sulfur Halides towards Transition‐Metal Compounds

“…Substitution of one of the sulfur bound fluorine atoms by NMe 2 again resulted in an energetically favored fluoride shift for {M[SF 2 (NMe 2 )](CO) n } [M=Ta, n =5 ( 133 a ); M=Re, n =4 ( 133 b ); M=Ir, n =3 ( 133 c )] and {CpM[SF 2 (NMe 2 )](CO) n } [Cp=η 5 ‐C 5 H 5 ; M=Cr ( 134 a ), Mo ( 134 b ), W ( 134 c ), n =2; M=Os, n =1 ( 134 d ); M=Pt, n =0 ( 134 e )] to yield the respective {[M](F)[SF(NMe 2 )]} complexes . Furthermore, calculations on the general feasibility of generating SF 2 ligands indicate a certain stability of [Fe 2 (μ‐SF 2 ) 2 (CO) n ] [ n =8 ( 135 a ), 7 ( 135 b )] and [Cp 2 Fe 2 (μ‐SF 2 )(CO) 4 ] ( 136 ), whereas in the mononuclear iron carbonyl complexes a fluoride migration is energetically favored . For the isomers [Cp 2 Fe 2 (SF 2 )(μ‐SF 2 )(CO) 3 ] ( 137 ) and [Cp 2 Fe 2 (SF 3 )(μ‐SF)(CO) 3 ] ( 138 ) the latter was shown to be lower in energy …”

Fluorine shifts from sulfur to metal in difluorosulfane complexes of cyclopentadienyl iron carbonyl: incompatibility of sulfur–fluorine bonds with iron–iron bonds

“…For this reason diuorosulfane metal complexes have not yet been synthesized. However, in order to explore the potential of diuorosulfane metal complexes, theoretical studies have been performed on diuorosulfane iron carbonyl complexes of the type Fe 15 In general, SF 2 complexes were found to be disfavored with respect to uorine migration from sulfur to the metal to give metal complexes containing separate SF and F ligands. It thus appears that the uorinating properties of the SF 2 ligand, like those of the SF 3 ligand, are too strong to be compatible with many transition metal systems.…”