Syntheses and crystallographic studies of [Ir(η5-C5Me5)(L)(RF)I] (L = CO, PMe3; RF = CF2CF3, CF2CF2CF3, CF2C6F5, CF(CF3)2) complexes. Cone and solid angle steric parameters for perfluoroalkyl ligands

Half-sandwich iridium complexes—Synthesis and applications in catalysis

“…Ir(I) complexes are also excellent precursors for half-sandwich iridium complex synthesis. Thus, oxidative addition of perfluoroalkyl iodides to the Ir(I) complexes Cp*Ir(CO) 2 37 gives the Ir(III) complexes 38 in good yield (Table 4, entry 1) [30]. Subsequent substitution of CO with trimethylphosphine affords Cp*Ir(R F )(PMe 3 )I.…”

Conversion of Carbon–Fluorine Bonds α to Transition Metal Centers to Carbon–Hydrogen, Carbon–Carbon, and Carbon–Heteroatom Bonds

“…These angular relationships are always found in the crystallographic structure of these molecules and make steric issues between the R, R F and PMe 3 ligands more important than those between any of these ligands and Cp*, even though Cp* is the ligand of largest cone angle. [189] Consequently, a position between the R and PMe 3 ligands (conformer C) is the least energetically favorable for the CF 3 (or other R F ) substituent attached to the α-carbon, and this group almost invariably occupies the region of space between PMe 3 and Cp* (conformer A rather than conformer B), perhaps because of the longer Ir-P bond compared to the Ir-R bond. The single exception to this rule involves the hydride complexes, in which the R F group sits between Cp* and H (conformer B), presumably as a result of the small steric demand of the hydride ligand.…”

The First Example of a Bis(trifluoromethyl)carbene Transition‐Metal Complex and Its Reduction to a Perfluoroallene Complex

“…Careful two-electron reduction of perfluoroisopropyl complex 7 [15] in thf by using Na/Pb alloy (Na ca.10 %) afforded bis(trifluoromethyl)carbene complex 8 in 87 % yield as a yellow, crystalline, sublimable, air-stable compound, unambiguously characterized by a single-crystal X-ray diffraction study. An ORTEP is shown in Figure 1 (Figure 1).…”

“…An ORTEP is shown in Figure 1 (Figure 1). The Ir-C double bond length of 1.928(7) Å is significantly shorter than the Ir-C single bond in 7 [2.11(3) Å] [15] and slightly longer than the double bond in its difluorocarbene analogue 2 [1.855(13) Å]. [10] Not unexpectedly, the CF 3 -Ir-CF 3 angle in 8 [110.0(6)°] is substantially larger than the F-C-F angle in 2 [103.5(10)°].…”