Intermolecular Migratory Insertion of Unactivated Olefins into Palladium–Nitrogen Bonds. Steric and Electronic Effects on the Rate of Migratory Insertion

2011 ◽  
Vol 133 (39) ◽  
pp. 15661-15673 ◽  
Author(s):  
Patrick S. Hanley ◽  
John F. Hartwig
Keyword(s):  
Electronic Effects ◽  
Migratory Insertion ◽  
Nitrogen Bonds

Factors Promoting Alkene Migratory Insertion into Metal-Nitrogen Bond during Hydroamination in Recent Studies

2021 ◽  
Vol 18 ◽  
Author(s):  
Wenlai Han
Keyword(s):  
Transition Metal ◽  
Late Transition Metal ◽  
Electronic Effects ◽  
Metal Centers ◽  
Unsaturated Bond ◽  
Factors Influencing ◽  
Migratory Insertion ◽  
Late Transition ◽  
Metal Catalyzed ◽  
Nitrogen Bond

: Migratory insertion is a fundamental organometallic transformation that enables the functionalization of an unsaturated bond. Recent reports on catalytic hydroamination provide evidence that supports an intermolecular migratory insertion pathway featuring alkene insertion into metal-nitrogen (M-N) bonds. This article presents factors influencing the rate of migratory insertion in late-transition metal-catalyzed hydroamination, including steric and electronic effects from ligands, alkenes, and metal centers, along with stabilization from coordinated amine intermediates and ordered transition states.

scholarly journals Migratory Insertion of Alkenes into Metal-Oxygen and Metal-Nitrogen Bonds

2013 ◽  
Vol 52 (33) ◽  
pp. 8510-8525 ◽  
Author(s):  
Patrick S. Hanley ◽  
John F. Hartwig
Keyword(s):  
Migratory Insertion ◽  
Nitrogen Bonds

Electronic effects in multicenter rearrangements of compounds with nitrogen-nitrogen bonds

1977 ◽  
Vol 42 (18) ◽  
pp. 3096-3097 ◽  
Author(s):  
James H. Cooley ◽  
Dennis M. Stone ◽  
Hiro Oguri
Keyword(s):  
Electronic Effects ◽  
Nitrogen Bonds

ChemInform Abstract: Migratory Insertion of Alkenes into Metal-Oxygen and Metal-Nitrogen Bonds

ChemInform ◽  
2013 ◽  
Vol 44 (44) ◽  
pp. no-no
Author(s):  
Patrick S. Hanley ◽  
John F. Hartwig
Keyword(s):  
Migratory Insertion ◽  
Nitrogen Bonds

On the Crystal Chemistry of Inorganic Nitrides: Crystal-Chemical Parameters and Opportunities in the Exploration of Their Compositional Space

2020 ◽  
Author(s):  
Olivier Charles Gagné
Keyword(s):  
Functional Properties ◽  
A Priori ◽  
Lone Pair ◽  
Length Variation ◽  
Electronic Effects ◽  
Statistical Knowledge ◽  
Redox Active ◽  
Multiply Bonded ◽  
Jahn Teller ◽  
Compositional Space

The scarcity of nitrogen in Earth’s crust, combined with challenging synthesis, have made inorganic nitrides a relatively-unexplored class of compounds compared to their naturally-abundant oxide counterparts. To facilitate exploration of their compositional space via <i>a priori</i> modeling, and to help <i>a posteriori</i> structure verification not limited to inferring the oxidation state of redox-active cations, we derive a suite of bond-valence parameters and Lewis-acid strength values for 76 cations observed bonding to N<sup>3-</sup>, and further outline a baseline statistical knowledge of bond lengths for these compounds. We examine structural and electronic effects responsible for the functional properties and anomalous bonding behavior of inorganic nitrides, and identify promising venues for exploring uncharted compositional spaces beyond the reach of high-throughput computational methods. We find that many mechanisms of bond-length variation ubiquitous to oxide and oxysalt compounds (e.g., lone-pair stereoactivity, the Jahn-Teller and pseudo Jahn-Teller effects) are similarly pervasive in inorganic nitrides, and are occasionally observed to result in greater distortion magnitude than their oxide counterparts. We identify inorganic nitrides with multiply-bonded metal ions as a promising venue in heterogeneous catalysis, e.g. in the development of a post-Haber-Bosch process proceeding at milder reaction conditions, thus representing further opportunity in the thriving exploration of the functional properties of this emerging class of materials.<br>

The Nature of S-N Bonding in Sulfonamides and Related Compounds: Insights into π-Bonding Contributions from Sulfur K-Edge XAS

2020 ◽  
Author(s):  
Tulin Okbinoglu ◽  
Pierre Kennepohl
Keyword(s):  
Density Functional ◽  
Chemical Properties ◽  
Functional Theory ◽  
Rotational Barriers ◽  
Td Dft ◽  
Nitrogen Bonds ◽  
X Ray Absorption ◽  
Related Compounds ◽  
And Chemical Properties

Molecules containing sulfur-nitrogen bonds, like sulfonamides, have long been of interest due to their many uses and chemical properties. Understanding the factors that cause sulfonamide reactivity is important, yet their continues to be controversy regarding the relevance of S-N π bonding in describing these species. In this paper, we use sulfur K-edge x-ray absorption spectroscopy (XAS) in conjunction with density functional theory (DFT) to explore the role of S<sub>3p</sub> contributions to π-bonding in sulfonamides, sulfinamides and sulfenamides. We explore the nature of electron distribution of the sulfur atom and its nearest neighbors and extend the scope to explore the effects on rotational barriers along the sulfur-nitrogen axis. The experimental XAS data together with TD-DFT calculations confirm that sulfonamides, and the other sulfinated amides in this series, have essentially no S-N π bonding involving S<sub>3p</sub> contributions and that electron repulsion and is the dominant force that affect rotational barriers.

NO Migratory Insertion into Ruthenium–Aryl Bond with a Hydridotris(pyrazolyl)borato Ligand

2021 ◽  
Vol 40 (3) ◽  
pp. 302-305
Author(s):  
Yasuhiro Arikawa ◽  
Motoki Yamada ◽  
Nobuko Takemoto ◽  
Shinnosuke Horiuchi ◽  
Eri Sakuda ◽  
...  
Keyword(s):  
Migratory Insertion
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