Synthesis and Reactivity of Iridium(I) Fluorido Complexes: Oxidative Addition of SF₄ at trans‐[Ir(F)(CO)(PEt₃)₂]

Abstract

The facile access to the Vaska type fluorido complexes trans‐[Ir(F)(CO)(PR3)2] [6: R = Et, 7: R = Ph, 8: R = iPr, 9: R = Cy, 10: R = tBu] was achieved by halide exchange at trans‐[Ir(Cl)(CO)(PR3)2] (1–5) with Me4NF. Furthermore, the reaction of complex 6 with SF4 gave cis,trans‐[Ir(F)2(SF3)(CO)(PEt3)2] (11), whereas 8–10 did not react. Reactivity studies revealed that 11 can selectively be manipulated at the sulfur atom by hydrolysis or fluoride abstraction to give cis,trans‐[Ir(F)2(SOF)(CO)(PEt3)2] (12) and cis,trans‐[Ir(F)2(SF2)(CO)(PEt3)2][AsF6] (13), respectively.

Fluorination Reactions at a Platinum Carbene Complex: Reaction Routes to SF3, S(=O)F and Fluorido Complexes

“…The above mentioned trigonal‐bipyramidal geometry at the sulfur atom was also confirmed by DFT calculations of 2 (BP86/def2‐SVP) [13d–f] . The frontier orbital analysis revealed that the electron pair is reflected by the HOMO (Figure 2).…”

“…The above mentioned trigonal‐bipyramidal geometry at the sulfur atom was also confirmed by DFT calculations of 2 (BP86/def2‐SVP). [ 13d , 13e , 13f ] The frontier orbital analysis revealed that the electron pair is reflected by the HOMO (Figure 2 ). Hence, the λ 4 ‐trifluoro sulfanyl ligand can be considered as an one‐electron donor or two‐electron donor, when the sulfanyl group is considered to be anionic.…”

Reactivity of Xantphos‐Type Rhodium Complexes Towards SF4: SF3 Versus SF2 Complex Generation

“…The signal at lower field appears as a triplet of doublets of doublets ( 3 J F,P =28 Hz, 3 J F,F =19 Hz, 2 J F,Rh =12 Hz) and can be assigned to the sulfur‐bound fluorine atoms of the SF 2 ligand. The coupling constants are consistent with these of other cationic SF 2 transition metal complexes [4a,e,f,i] . The broad doublet of triplets ( 2 J F,Rh =176 Hz 3 J F,F =20 Hz) at high field can be attributed to a metal‐bound fluorine atom and shows couplings to rhodium and the fluorine atoms bound to the SF 2 ligand, which is also confirmed by 19 F, 19 F‐COSY NMR spectroscopy (Supporting Information, Figure S33) [4g,7] …”

“…The two broad low‐field shifted signals correspond to resonances of SF 4 , which is presumably generated by fluoride abstraction from the SF 5 anion in 6 [15] . The SF 2 ligand can be assigned to the broad triplet at δ =−31.6 ppm, which is in a typical range for SF 2 ligands [4a,e,f,i] . Upon heating up to room temperature the signal sharpens to a triplet of doublets with coupling constants 3 J F,P =27 Hz and 2 J F,Rh =8 Hz.…”

“…At 193 K the 31 P{ 1 H} NMR spectrum of 6 displays an AB pattern, which was simulated (Figure 3). The inequivalent phosphorus atoms P a and P b couple to rhodium ( 1 J Pa,Rh =103.3 Hz, P b : 1 J Pb,Rh =95.5 Hz), [9a,11,12] to each other ( 2 J Pa,Pb =292.0 Hz) [4a,b,i,12b,13] and to one of the three sulfur bound fluorine atoms, with coupling constants 3 J Pa,Fa’ =28.4 Hz and 3 J Pb,Fa’ =37.1 Hz. The signal in the 13 C{ 1 H} NMR spectrum of 6 at δ =7.8 ppm is significantly low‐field shifted by about 28 ppm when compared to the corresponding resonance for 5 .…”