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1. Single-conformation spectroscopy of cold, protonated ^D PG-containing peptides: switching β-turn types and formation of a sequential type II/II′ double β-turn

   https://doi.org/10.1039/D1CP04852J  

   Lawler, John T. ; Harrilal, Christopher P. ; DeBlase, Andrew F. ; Sibert, Edwin L. ; McLuckey, Scott A. ; Zwier, Timothy S. ( January 2022 , Physical Chemistry Chemical Physics)

   d -Proline ( D Pro, D P) is widely utilized to form β-hairpin loops in engineered peptides that would otherwise be unstructured, most often as part of a D PG sub-unit that forms a β-turn. To observe whether D PG facilitated this effect in short protonated peptides, conformation specific IR–UV double resonance photofragment spectra of the cold (∼10 K) protonated D P and L P diastereomers of the pentapeptide YAPGA was carried out in the hydride stretch (2800–3700 cm −1 ) and amide I/II (1400–1800 cm −1 ) regions. A model localized Hamiltonian was developed to better describe the 1600–1800more »cm −1 region commonly associated with the amide I vibrations. The CO stretch fundamentals experience extensive mixing with the N–H bending fundamentals of the NH 3 + group in these protonated peptides. The model Hamiltonian accounts for experiment in quantitative detail. In the D P diastereomer, all the population is funneled into a single conformer which presented as a type II β-turn with A and D P in the i + 1 and i + 2 positions, respectively. This structure was not the anticipated type II′ β-turn across D PG that we had hypothesized based on solution-phase propensities. Analysis of the conformational energy landscape shows that both steric and charge-induced effects play a role in the preferred formation of the type II β-turn. In contrast, the L P isomer forms three conformations with very different structures, none of which were type II/II′ β-turns, confirming that L PG is not a β-turn former. Finally, single-conformation spectroscopy was also carried out on the extended peptide [YAA D PGAAA + H] + to determine whether moving the protonated N-terminus further from D PG would lead to β-hairpin formation. Despite funneling its entire population into a single peptide backbone structure, the assigned structure is not a β-hairpin, but a concatenated type II/type II′ double β-turn that displaces the peptide backbone laterally by about 7.5 Å, but leaves the backbone oriented in its original direction.« less
2. Electrochemical C–H bond activation via cationic iridium hydride pincer complexes

   https://doi.org/10.1039/C9SC03076J  

   Lindley, Brian M. ; Walden, Andrew G. ; Brasacchio, Ann Marie ; Casuras, Andrea ; Lease, Nicholas ; Chen, Chun-Hsing ; Goldman, Alan S. ; Miller, Alexander J. ( January 2019 , Chemical Science)

   A C–H bond activation strategy based on electrochemical activation of a metal hydride is introduced. Electrochemical oxidation of ( tBu4 PCP)IrH 4 ( tBu4 PCP is [1,3-( t Bu 2 PCH 2 )-C 6 H 3 ] − ) in the presence of pyridine derivatives generates cationic Ir hydride complexes of the type [( tBu4 PCP)IrH(L)] + (where L = pyridine, 2,6-lutidine, or 2-phenylpyridine). Facile deprotonation of [( tBu4 PCP)IrH(2,6-lutidine)] + with the phosphazene base tert -butylimino-tris(pyrrolidino)phosphorane, t BuP 1 (pyrr), results in selective C–H activation of 1,2-difluorobenzene (1,2-DFB) solvent to generate ( tBu4 PCP)Ir(H)(2,3-C 6 F 2 H 3more »). The overall electrochemical C–H activation reaction proceeds at room temperature without need for chemical activation by a sacrificial alkene hydrogen acceptor. This rare example of undirected electrochemical C–H activation holds promise for the development of future catalytic processes.« less
3. Ionization of gold (γ-methoxy)vinyl complexes generates reactive gold vinyl carbene complexes

   https://doi.org/10.1039/c9sc01574d  

   Kim, Nana ; Widenhoefer, Ross A. ( June 2019 , Chemical Science)

   Cationic gold vinyl carbene/allylic cation complexes of the form ( E )-[(L)AuC(H)C(H)CAr 2 ] + OTf − {L = IPr, Ar = Ph [( E )- 5a ], L = IPr, Ar = 4-C 6 H 4 OMe [( E )- 5b ], L = P( t -Bu) 2 o -biphenyl, Ar = 4-C 6 H 4 OMe [( E )- 5c ]} were generated in solution via Lewis acid-mediated ionization of the corresponding gold (γ-methoxy)vinyl complexes ( E )-(L)AuC(H)C(H)C(OMe)Ar 2 at or below −95 °C. Complexes ( E )- 5b and ( E )- 5c were fully characterized inmore »solution employing multinuclear NMR spectroscopy, which established the predominant contribution of the aurated allylic cation resonance structure and the significant distribution of positive charge into the γ-anisyl rings. Complex ( E )- 5b reacted rapidly at −95 °C with neutral two-electron, hydride, and oxygen atom donors exclusively at the C1 position of the vinyl carbene moiety and with p -methoxystyrene to form the corresponding vinylcyclopropane. In the absence of nucleophile ( E )- 5a decomposed predominantly via intermolecular carbene dimerization whereas formation of 1-aryl-5-methoxy indene upon ionization of ( Z )-(IPr)AuC(H)C(H)C(OMe)(4-C 6 H 4 OMe) 2 [( Z )- 6b ] implicated an intramolecular Friedel–Crafts or electrocyclic Nazarov pathway for the decomposition of the unobserved vinyl carbene complex ( Z )-[(IPr)AuC(H)C(H)C(4-C 6 H 4 OMe) 2 ] + OTf − [( Z )- 5b ].« less
4. The Trajectory of the (η 5-Cyclopentadienyl)cobalt-Mediated Cycloisomerization of Ene-Yne-Ene-Type Allyl Propargylic Ethers to Furans: A DFT Appraisal

   https://doi.org/10.1055/a-1645-2632  

   Wong, Jonathan J. ; Chen, Xiangyang ; Houk, Kendall N. ; Vollhardt, K. Peter ( October 2021 , Synthesis)

   Abstract The mechanisms by which the complexes CpCoL2 (Cp = C5H5; L = CO or CH2=CH2) mediate the cycloisomerizations of α,δ,ω-enynenes containing allylic ether linkages are probed by DFT methods. The outcomes corroborate experimental results and provide energetic and structural details of the trajectories leading to 3-(oxacyclopentyl or cycloalkyl)furans via the intermediacy of isolable CpCo-η 4-dienes. They comprise initial stereoselective complexation of one of the double bonds and the triple bond, rate-determining oxidative coupling to a triplet 16e cobalta-2-cyclopentene, and terminal double bond docking, followed by stereocontrolled insertion to assemble intermediate cis- and trans-fused triplet cobalta-4-cycloheptenes. A common indicator ofmore »the energetic facility of the latter is the extent of parallel alignment of the alkene moiety and its target Co–Cα bond. The cobalta-4-cycloheptenes transform further by β-hydride elimination–reductive elimination to furnish CpCo-η 4-dienes, which are sufficiently kinetically protected to allow for their experimental observation. The cascade continues through cobalt-mediated hydride shifts and dissociation of the aromatic furan ring. The findings in silico with respect to the stereo-, regio-, and chemoselectivity are in consonance with those obtained in vitro.« less
5. Mixed-dimensional InAs nanowire on layered molybdenum disulfide heterostructures via selective-area van der Waals epitaxy

   https://doi.org/10.1039/D0NA00768D  

   Baboli, Mohadeseh A. ; Abrand, Alireza ; Burke, Robert A. ; Fedorenko, Anastasiia ; Wilhelm, Thomas S. ; Polly, Stephen J. ; Dubey, Madan ; Hubbard, Seth M. ; Mohseni, Parsian K. ( May 2021 , Nanoscale Advances)

   Self-assembly of vertically aligned III–V semiconductor nanowires (NWs) on two-dimensional (2D) van der Waals (vdW) nanomaterials allows for integration of novel mixed-dimensional nanosystems with unique properties for optoelectronic and nanoelectronic device applications. Here, selective-area vdW epitaxy (SA-vdWE) of InAs NWs on isolated 2D molybdenum disulfide (MoS 2 ) domains is reported for the first time. The MOCVD growth parameter space ( i.e. , V/III ratio, growth temperature, and total molar flow rates of metalorganic and hydride precursors) is explored to achieve pattern-free positioning of single NWs on isolated multi-layer MoS 2 micro-plates with one-to-one NW-to-MoS 2 domain placement. The introductionmore »of a pre-growth poly- l -lysine surface treatment is highlighted as a necessary step for mitigation of InAs nucleation along the edges of triangular MoS 2 domains and for NW growth along the interior region of 2D micro-plates. Analysis of NW crystal structures formed under the optimal SA-vdWE condition revealed a disordered combination of wurtzite and zinc-blend phases. A transformation of the NW sidewall faceting structure is observed, resulting from simultaneous radial overgrowth during axial NW synthesis. A common lattice arrangement between axially-grown InAs NW core segments and MoS 2 domains is described as the epitaxial basis for vertical NW growth. A model is proposed for a common InAs/MoS 2 sub-lattice structure, consisting of three multiples of the cubic InAs unit cell along the [21̄1̄] direction, commensurately aligned with a 14-fold multiple of the Mo–Mo (or S–S) spacing along the [101̄0] direction of MoS 2 hexagonal lattice. The SA-vdWE growth mode described here enables controlled hybrid integration of mixed-dimensional III–V-on-2D heterostructures as novel nanosystems for applications in optoelectronics, nanoelectronics, and quantum enabling technologies.« less