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1.
J Am Chem Soc ; 139(18): 6338-6350, 2017 05 10.
Article in English | MEDLINE | ID: mdl-28418249

ABSTRACT

NaBArF4 (sodium tetrakis[(3,5-trifluoromethyl)phenyl]borate) was found to catalyze reactions of (Phebox)IrIII(acetate) (Phebox = 2,6-bis(4,4-dimethyloxazolinyl)-3,5-dimethylphenyl) complexes, including (i) ß-H elimination of (Phebox)Ir(OAc)(n-alkyl) to give (Phebox)Ir(OAc)(H) and the microscopic reverse, alkene insertion into the Ir-H bond of (Phebox)Ir(OAc)(H), and (ii) hydrogenolysis of the Ir-alkyl bond of (Phebox)Ir(OAc)(n-alkyl) and the microscopic reverse, C-H activation by (Phebox)Ir(OAc)(H), as indicated by H/D exchange experiments. For example, ß-H elimination of (Phebox)Ir(OAc)(n-octyl) (2-Oc) proceeded on a time scale of minutes at -15 °C in the presence of (0.4 mM) NaBArF4 as compared with a very slow reaction at 125 °C in the absence of NaBArF4. In addition to NaBArF4, other Lewis acids are also effective. Density functional theory calculations capture the effect of the Na+ cation and indicate that it operates primarily by promoting κ2-κ1 dechelation of the acetate anion, which opens the coordination site needed to allow the observed reaction to proceed. In accord with the effect on these individual stoichiometric reactions, NaBArF4 was also found to cocatalyze, with (Phebox)Ir(OAc)(H), the acceptorless dehydrogenation of n-dodecane.

2.
Chem Sci ; 7(4): 2579-2586, 2016 Apr 21.
Article in English | MEDLINE | ID: mdl-28660029

ABSTRACT

A rhodium complex based on the bis-phosphine carbazolide pincer ligand was investigated in the context of alkane dehydrogenation and in comparison with its iridium analogue. (carb-PNP)RhH2 was found to catalyze cyclooctane/t-butylethylene (COA/TBE) transfer dehydrogenation with a turnover frequency up to 10 min-1 and turnover numbers up to 340, in marked contrast with the inactive Ir analogue. TONs were limited by catalyst decomposition. Through a combination of mechanistic, experimental and computational (DFT) studies the difference between the Rh and Ir analogues was found to be attributable to the much greater accessibility of the 14-electron (carb-PNP)M(i) fragment in the case of Rh. In contrast, Ir is more strongly biased toward the M(iii) oxidation state. Thus (carb-PNP)RhH2 but not (carb-PNP)IrH2 can be dehydrogenated by sacrificial hydrogen acceptors, particularly TBE. The rate-limiting segment of the (carb-PNP)Rh-catalyzed COA/TBE transfer dehydrogenation cycle is found to be the dehydrogenation of COA. Within this segment, the rate-determining step is calculated to be (carb-PNP)Rh(cyclooctyl)(H) undergoing formation of a ß-H agostic intermediate, while the reverse step (loss of a ß-H agostic interaction) is rate-limiting for hydrogenation of the acceptors TBE and ethylene. Such a step has not previously been proposed as rate-limiting in the context of alkane dehydrogenation, nor, to our knowledge, has the reverse step been proposed as rate-limiting for olefin hydrogenation.

3.
Dalton Trans ; 43(43): 16354-65, 2014 Nov 21.
Article in English | MEDLINE | ID: mdl-25250874

ABSTRACT

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.


Subject(s)
Carbon/chemistry , Coordination Complexes/chemistry , Hydrogen/chemistry , Iridium/chemistry , Biphenyl Compounds/chemistry , Crystallography, X-Ray , Ligands , Molecular Conformation , Thermodynamics
4.
J Am Chem Soc ; 136(18): 6672-83, 2014 May 07.
Article in English | MEDLINE | ID: mdl-24746026

ABSTRACT

New carbazolide-based iridium pincer complexes ((carb)PNP)Ir(C2H4), 3a, and ((carb)PNP)Ir(H)2, 3b, have been prepared and characterized. The dihydride, 3b, reacts with ethylene to yield the cis-dihydride ethylene complex cis-((carb)PNP)Ir(C2H4)(H)2. Under ethylene this complex reacts slowly at 70 °C to yield ethane and the ethylene complex, 3a. Kinetic analysis establishes that the reaction rate is dependent on ethylene concentration and labeling studies show reversible migratory insertion to form an ethyl hydride complex prior to formation of 3a. Exposure of cis-((carb)PNP)Ir(C2H4)(H)2 to hydrogen results in very rapid formation of ethane and dihydride, 3b. DFT analysis suggests that ethane elimination from the ethyl hydride complex is assisted by ethylene through formation of ((carb)PNP)Ir(H)(Et)(C2H4) and by H2 through formation of ((carb)PNP)Ir(H)(Et)(H2). Elimination of ethane from Ir(III) complex ((carb)PNP)Ir(H)(Et)(H2) is calculated to proceed through an Ir(V) complex ((carb)PNP)Ir(H)3(Et) which reductively eliminates ethane with a very low barrier to return to the Ir(III) dihydride, 3b. Under catalytic hydrogenation conditions (C2H4/H2), cis-((carb)PNP)Ir(C2H4)(H)2 is the catalyst resting state, and the catalysis proceeds via an Ir(III)/Ir(V)/Ir(III) cycle. This is in sharp contrast to isoelectronic (PCP)Ir systems in which hydrogenation proceeds through an Ir(III)/Ir(I)/Ir(III) cycle. The basis for this remarkable difference is discussed.

5.
J Am Chem Soc ; 135(40): 15062-70, 2013 Oct 09.
Article in English | MEDLINE | ID: mdl-24028199

ABSTRACT

Aryl alkyl ethers, which are widely used throughout the chemical industry, are typically produced via the Williamson ether synthesis. Olefin hydroaryloxylation potentially offers a much more atom-economical alternative. Known acidic catalysts for hydroaryloxylation, however, afford very poor selectivity. We report the organometallic-catalyzed intermolecular hydroaryloxylation of unactivated olefins by iridium "pincer" complexes. These catalysts do not operate via the hidden Brønsted acid pathway common to previously developed transition-metal-based catalysts. The reaction is proposed to proceed via olefin insertion into an iridium-alkoxide bond, followed by rate-determining C-H reductive elimination to yield the ether product. The reaction is highly chemo- and regioselective and offers a new approach to the atom-economical synthesis of industrially important ethers and, potentially, a wide range of other oxygenates.

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