Insertion of CS₂ into Iridium–Fluorine Bonds

Abstract

CS2 jumps in: CF bond formation occurs by reactions of the fluorido complexes trans-[Ir(Ar(F) )(F)(H)(PiPr3 )2 ] (Ar(F) =4-C5 NF4 ; see scheme) with CS2 to form the fluorodithiocarbonato species trans-[Ir(Ar(F) )(H)(κ(2) -(S,S)-S2 CF)(PiPr3 )2 ]. DFT studies suggest an unprecedented concerted metathesis-like mechanism for the CF bond-formation step in which CS2 inserts into the IrF bond.

The Versatile Behavior of Platinum Alkyne Complexes towards XeF2: Formation of Fluorovinyl and Fluorido Complexes

“…The resonance for the metal‐bound fluorido ligand appears in the 19 F{ 1 H} NMR spectrum (Figure ) as a doublet of doublets at high field with 195 Pt satellites ( δ =−206.9 ppm, 4 J (F,F)=3, 2 J (P,F trans )=179, 1 J (Pt,F)=156 Hz). The chemical shift as well as the coupling constant are characteristic of a transition‐metal‐bound fluorido ligand . The β‐fluorine atom causes a doublet with 195 Pt satellites at δ =−91.9 ppm ( 4 J (F,F)=3, 3 J (Pt,F)=260 Hz), which appears in the typical area for a β‐fluorovinyl ligand .…”

Tethered Alkylidenes for REMP from Carbon Disulfide Cleavage

“…Signaling substantial back-donation of electron density from the tungsten center into the π* orbital of the ligated CS unit, the coordinated S2–C32 bond elongates to 1.6986(14) Å, and the S1–C32–S2 angle bends to 138.94(9)° (CS 2 : CS = 1.552(3) Å; SCS = 180°) . These structural features are consistent with related η 2 -CS 2 complexes. − To the best of our knowledge, complex 8 is the first structurally characterized complex of a tungsten η 2 -( S , C ) coordinated CS 2 . Though Schenk and co-workers reported the initial synthesis of a series of complexes with η 2 -( S , C ) coordination to a tungsten center [W­(CO) 3 (diphosphine)­(CS 2 )] and studied their reactivity toward various nucleophiles and electrophiles, no X-ray structural data exists. − …”

Synthesis of an Iridium Peroxido Complex and Its Reactivity Towards Brønsted Acids

“…In contrast, 3a gives trans ‐[Ir{κ 2 ‐ O C(O) O }(4‐C 5 F 4 N)(CN t Bu)(P i Pr 3 ) 2 ] ( 6 ), trans , trans ‐[Ir(4‐C 5 F 4 N)(H) 2 (CN t Bu)(P i Pr 3 ) 2 ] ( 7a ), cis , trans ‐[Ir(4‐C 5 F 4 N)(H) 2 (CN t Bu)(P i Pr 3 ) 2 ] ( 9a ), and phosphine oxide. All iridium and rhodium complexes feature the tetrafluoropyridyl ligand, which is able to stabilize unique complexes 17,28a,31,33…”