Square‐Planar Iridium(II) and Iridium(III) Amido Complexes Stabilized by a PNP Pincer Ligand

Abstract

Squaring the circle: the novel dienamido pincer ligand N(CHCHPtBu(2))(2)(-) affords the isolation of the unusual square-planar iridium(II) and iridium(III) amido complexes [IrCl{N(CHCHPtBu(2))(2)}](n) (n=0 (1), +1 (2)). In contrast, the corresponding iridium(I) complex of the redox series (n=-1) is surprisingly unstable. The diamagnetism of 2 is attributed to strong N→Ir π donation.

Four-Component Relativistic Density Functional Theory Calculations of EPRg- and Hyperfine-Coupling Tensors Using Hybrid Functionals: Validation on Transition-Metal Complexes with Large Tensor Anisotropies and Higher-Order Spin–Orbit Effects

“…[110][111][112][113][114][115] These larger complexes also demonstrate the efficiency of the 4c-mDKS approach, as they contain up to 133 atoms and 607 electrons in the case of [PtI2(IPr)2] + . For this complex, we indeed reduced the computational effort by using the somewhat smaller Hirao/IGLO-II basis set combination (leading to 2960 Cartesian one-component GTOs).…”

[IrCl{N(CHCHPtBu2)2}]−: a versatile source of the IrI(PNP) pincer platform

“…Complex 2, Na/Hg and KC 8 were prepared according to published procedures. 14,41,42 Elemental analyses were obtained from the Analytical Laboratories at Friedrich-Alexander-University and Georg-August-University, respectively. IR spectra were recorded as nujol mulls between KBr disks using a JASCO FT/ IR 4100 Spectrometer.…”

A Terminal Iridium Oxo Complex with a Triplet Ground State

“…Salt metathesis of [IrCl(PNP)] (4) [13] with NaOH in THF/ H 2 O( 2:1) afforded the iridium(II) hydroxide complex [Ir-(OH)(PNP)] (5)i n9 1% isolated yield (Scheme 1). [14] Characterization of 5 by ESI-MS and X-ray crystallography ( Figure 2) confirmed the formation of arare,terminal iridium hydroxide complex. [15] Electrochemical examination in THF by cyclic voltammetry (CV) showed reversible reduction (E o = À2.11 V; vs.F c/Fc + )a nd oxidation (E o = À0.37 V) waves on the CV timescale (v = 50-1000 mV s À1 ).…”