Matthew Nava
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View article: Reversible room temperature heterolytic activation of vinylic sp2 C–H bonds at a gallium center
Reversible room temperature heterolytic activation of vinylic sp2 C–H bonds at a gallium center Open
The identification of molecular design principles which enable the activation of strong nonpolar bonds remains an open challenge, particularly for main-group elements. Inspired by reports of metal-framework cooperativity in gallium contain…
View article: Metal–ligand cooperativity enables zero-valent metal transfer
Metal–ligand cooperativity enables zero-valent metal transfer Open
Group 13 aminoxy complexes, (L)E(TEMPO) 3 (TEMPO = 2,2,6,6-tetramethylpiperidine 1-oxyl; L = THF (tetrahydrofuran) or Py (pyridine); E = Al, Ga, In), display ambiphilic reactivity with H 2 and function as synthons for the preparation of ma…
View article: Metal-Ligand Cooperativity Enables Zero-Valent Metal Transfer
Metal-Ligand Cooperativity Enables Zero-Valent Metal Transfer Open
Group 13 TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) complexes of the form (L)E(TEMPO)3 (L=THF (tetrahydrofuran) or Py (pyridine); E = Al, Ga, In) were prepared and structurally characterized. The complexes (THF)Ga(TEMPO)3 (1·THF) and (Py…
View article: Determination of Initial Rates of Lipopolysaccharide Transport
Determination of Initial Rates of Lipopolysaccharide Transport Open
Nonvesicular lipid trafficking pathways are an important process in every domain of life. The mechanisms of these processes are poorly understood in part due to the difficulty in kinetic characterization. One important class of glycolipids…
View article: The Coupling of Synthesis and Electrochemistry to Enable the Reversible Storage of Hydrogen as Metal Hydrides
The Coupling of Synthesis and Electrochemistry to Enable the Reversible Storage of Hydrogen as Metal Hydrides Open
Given its high gravimetric energy density and status as a clean fuel when derived from renewables, hydrogen (H2) is considered a premier candidate for energy storage; however, its low volumetric density limits its broader application. Chem…
View article: Electrophotocatalytic perfluoroalkylation by LMCT excitation of Ag(II) perfluoroalkyl carboxylates
Electrophotocatalytic perfluoroalkylation by LMCT excitation of Ag(II) perfluoroalkyl carboxylates Open
Molecular Ag(II) complexes are superoxidizing photoredox catalysts capable of generating radicals from redox-reticent substrates. In this work, we exploited the electrophilicity of Ag(II) centers in [Ag(bpy) 2 (TFA)][OTf] and Ag(bpy)(TFA) …
View article: Chemical Challenges that the Peroxide Dianion Presents to Rechargeable Lithium–Air Batteries
Chemical Challenges that the Peroxide Dianion Presents to Rechargeable Lithium–Air Batteries Open
Understanding the fundamental redox reactions and processes that occur in lithium–air and, more generally, metal–air batteries is important to the progress of this promising energy-storage technology. Knowledge of the chemistry of the pero…
View article: Lithium superoxide encapsulated in a benzoquinone anion matrix
Lithium superoxide encapsulated in a benzoquinone anion matrix Open
Significance Lithium superoxide (LiO 2 ) is an important intermediate in lithium–air batteries, a promising next-generation energy-storage platform. The conductivity, stability, and reactivity profiles of LiO 2 are thought to play a crucia…
View article: How Radical are ‘Radical’ Photocatalysts? A Closed-Shell Meisenheimer Complex is Identified as a Super-reducing Photoreagent
How Radical are ‘Radical’ Photocatalysts? A Closed-Shell Meisenheimer Complex is Identified as a Super-reducing Photoreagent Open
Super-reducing excited states have the potential to activate strong bonds, leading to unprecedented photoreactivity. Excited states of radical anions, accessed via reduction of a precatalyst followed by light absorption, have been proposed…
View article: How Radical are ‘Radical’ Photocatalysts? A Closed-Shell Meisenheimer Complex is Identified as a Super-reducing Photoreagent
How Radical are ‘Radical’ Photocatalysts? A Closed-Shell Meisenheimer Complex is Identified as a Super-reducing Photoreagent Open
Super-reducing excited states have the potential to activate strong bonds, leading to unprecedented photoreactivity. Excited states of radical anions, accessed via reduction of a precatalyst followed by light absorption, have been proposed…
View article: Synchrotron-Based High Resolution Far-Infrared Spectroscopy of <i>trans</i>-Butadiene
Synchrotron-Based High Resolution Far-Infrared Spectroscopy of <i>trans</i>-Butadiene Open
The high resolution far-infrared spectrum of trans-butadiene has been reinvestigated by Fourier-transform spectroscopy at two synchrotron radiation facilities, SOLEIL and the Canadian Light Source, at temperatures ranging from 50 to 340 K.…
View article: CCDC 1870937: Experimental Crystal Structure Determination
CCDC 1870937: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: CCDC 1870935: Experimental Crystal Structure Determination
CCDC 1870935: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: CCDC 1870936: Experimental Crystal Structure Determination
CCDC 1870936: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: Sulfur monoxide thermal release from an anthracene-based precursor, spectroscopic identification, and transfer reactivity
Sulfur monoxide thermal release from an anthracene-based precursor, spectroscopic identification, and transfer reactivity Open
Significance The generation of highly reactive molecules under controlled conditions is desirable, as it allows exploration of synthetic chemistry and enables spectroscopic studies of such elusive species. We report here on the synthesis a…
View article: CCDC 1567576: Experimental Crystal Structure Determination
CCDC 1567576: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: CCDC 1567577: Experimental Crystal Structure Determination
CCDC 1567577: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: The Molecular Structure of <i>gauche</i>‐1,3‐Butadiene: Experimental Establishment of Non‐planarity
The Molecular Structure of <i>gauche</i>‐1,3‐Butadiene: Experimental Establishment of Non‐planarity Open
The planarity of the second stable conformer of 1,3‐butadiene, the archetypal diene for the Diels–Alder reaction in which a planar conjugated diene and a dienophile combine to form a ring, is not established. The most recent high level cal…
View article: On the incompatibility of lithium–O<sub>2</sub> battery technology with CO<sub>2</sub>
On the incompatibility of lithium–O<sub>2</sub> battery technology with CO<sub>2</sub> Open
The peroxide dianion reacts with CO2 in polar aprotic organic media to afford the hydroperoxycarbonate and carbonate radical anions. These highly reactive species, if formed in lithium–O2 cells, can lead to cell degradation via oxidation o…
View article: CCDC 1552464: Experimental Crystal Structure Determination
CCDC 1552464: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: CCDC 1566922: Experimental Crystal Structure Determination
CCDC 1566922: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: CCDC 1566923: Experimental Crystal Structure Determination
CCDC 1566923: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: CCDC 1552463: Experimental Crystal Structure Determination
CCDC 1552463: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries
Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries Open
Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H₂S biochemistries, but its existence and stability in vivo remain controversial. We establish that HSNO is spontaneou…
View article: Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H
Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H Open
Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H[superscript 2]S biochemistries, but its existence and stability in vivo remain controversial. We establish that HSNO…
View article: A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion
A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion Open
Dibenzo-7-phosphanorbornadiene Ph3PC(H)PA (1, A = C14H10, anthracene) is reported here as a molecular precursor to phosphaethyne (HC≡P), produced together with anthracene and triphenylphosphine. HCP generated by thermolysis of 1 has been o…
View article: A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion
A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion Open
Dibenzo-7-phosphanorbornadiene Ph[subscript 3]PC(H)PA (1, A = C[subscript 14]H[subscript 10], anthracene) is reported here as a molecular precursor to phosphaethyne (HC≡P), produced together with anthracene and triphenylphosphine. HCP gene…
View article: CCDC 1473458: Experimental Crystal Structure Determination
CCDC 1473458: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …