We report that pincer-ligated iridium complexes undergo oxidative addition of the strained C-C bond of biphenylene. The sterically crowded species ((tBu)PCP)Ir ((R)PCP = κ(3)-1,3-C6H3(CH2PR2)2) initially reacts with biphenylene to selectively add the C(1)-H bond, to give a relatively stable aryl hydride complex. Upon heating at 125 °C for 24 h, full conversion to the C-C addition product, ((tBu)PCP)Ir(2,2'-biphenyl), is observed. The much less crowded ((iPr)PCP)Ir undergoes relatively rapid C-C addition at room temperature. The large difference in the apparent barriers to C-C addition is notable in view of the fact that the addition products are not particularly crowded, since the planar biphenyl unit adopts an orientation perpendicular to the plane of the (R)PCP ligands. Based on DFT calculations the large difference in the barriers to C-C addition can be explained in terms of a "tilted" transition state. In the transition state the biphenylene cyclobutadiene core is calculated to be strongly tilted (ca. 50°-60°) relative to its orientation in the product in the plane perpendicular to that of the PCP ligand; this tilt results in very short, unfavorable, non-bonding contacts with the t-butyl groups in the case of the (tBu)PCP ligand. The conclusions of the biphenylene studies are applied to interpret computational results for cleavage of the unstrained C-C bond of biphenyl by ((R)PCP)Ir.
The pincer-iridium fragment (PCP)Ir (PCP = κ-2,6-CH(CHPR)) has been found to catalyze the dehydrogenative coupling of vinyl arenes to afford predominantly (E,E)-1,4-diaryl-1,3-butadienes. The eliminated hydrogen can undergo addition to another molecule of vinyl arene, resulting in an overall disproportionation reaction with 1 equiv of ethyl arene formed for each equivalent of diarylbutadiene produced. Alternatively, sacrificial hydrogen acceptors (e.g., tert-butylethylene) can be added to the solution for this purpose. Diarylbutadienes are isolated in moderate to good yields, up to ca. 90% based on the disproportionation reaction. The results of DFT calculations and experiments with substituted styrenes indicate that the coupling proceeds via double C-H addition of a styrene molecule, at β-vinyl and ortho-aryl positions, to give an iridium(III) metalloindene intermediate; this intermediate then adds a β-vinyl C-H bond of a second styrene molecule before reductively eliminating product. Several metalloindene complexes have been isolated and crystallographically characterized. In accord with the proposed mechanism, substitution at the ortho-aryl positions of the styrene precludes dehydrogenative homocoupling. In the case of 2,4,6-trimethylstyrene, dehydrogenative coupling of β-vinyl and ortho-methyl C-H bonds affords dimethylindene, demonstrating that the dehydrogenative coupling is not limited to C(sp)-H bonds.
We have developed inorganic oxalate compounds ½PPh 3 ðCH 2 PhÞ½Mð2; 2 0-bipyridineÞ n ðoxalateÞ ð3−nÞ (n ¼ 1,2,3;M¼ Co, Fe, Cr) capable of acting as negative-tone extreme ultraviolet (EUV) resists. Two important trends are observed: (1) sensitivity increases with the number of oxalate ligands; (2) Cobalt and iron complexes exhibit greater sensitivity than analogous chromium complexes. Lithographic studies of the most successful compound, ½PPh 3 ðCH 2 PhÞ½Coð2; 2 0-bipyridineÞðoxalateÞ 2 , show that it can consistently achieve 20 nm h/p lines at doses approaching 30 mJ∕cm 2. Infrared, paramagnetic nuclear magnetic resonance, and cyclic voltammetric studies of this compound show that the reaction products of the EUV photochemistry are Co(II)(2,2'-bipyridine) (oxalate) and ½PPh 3 ðCH 2 PhÞ 2 ðoxalateÞ formed from the decomposition of one of the oxalate ligands into two equivalents each of carbon dioxide and electrons.
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