Long-range metal–metal coupling in transition-metal 5,10,15,20-tetraferrocenylporphyrins

2011 ◽  
Vol 35 (7) ◽  
pp. 1440 ◽  
Author(s):  
Gregory T. Rohde ◽  
Jared R. Sabin ◽  
Christopher D. Barrett ◽  
Victor N. Nemykin
Keyword(s):  
Transition Metal ◽  
Long Range ◽  
Metal Metal

scholarly journals 1st Row Transition Metal Aluminylene Complexes: Preparation, Properties and Bonding Analysis

2021 ◽  
Author(s):  
Richard Y Kong ◽  
Mark Crimmin
Keyword(s):  
Transition Metal ◽  
Ab Initio ◽  
Long Range ◽  
Short Range ◽  
Dispersion Interactions ◽  
Metal Centre ◽  
Bonding Analysis ◽  
Metal Metal ◽  
Spectroscopic Characterisation ◽  
Insight Into

<i>The synthesis and spectroscopic characterisation of eight new first-row transition metal (M = Cr, Mn, Fe, Co, Cu) aluminylene complexes is reported. DFT and ab<b> </b>initio calculations have been used to provide detailed insight into the metal–metal bond. The σ-donation and π-backdonation properties of the aluminylene ligand are evaluated via NBO and ETS-NOCV calculations. These calculations reveal that these ligands are strong σ-donors but also competent π-acceptors. These properties are not fixed but vary in response to the nature of the transition metal centre, suggesting that aluminylene fragments can modulate their bonding to accommodate both electron-rich and electron-poor transition metals. Ab initio<b> </b>DLPNO-CCSD(T) calculations show that dispersion plays an important role in stabilising these complexes. Both short-range and long-range dispersion interactions are identified. These results will likely inform the design of next-generation catalysts based on aluminium metalloligands. </i>

scholarly journals 1st Row Transition Metal Aluminylene Complexes: Preparation, Properties and Bonding Analysis

2021 ◽  
Author(s):  
Richard Y Kong ◽  
Mark Crimmin
Keyword(s):  
Transition Metal ◽  
Ab Initio ◽  
Long Range ◽  
Short Range ◽  
Dispersion Interactions ◽  
Metal Centre ◽  
Bonding Analysis ◽  
Metal Metal ◽  
Spectroscopic Characterisation ◽  
Insight Into

<i>The synthesis and spectroscopic characterisation of eight new first-row transition metal (M = Cr, Mn, Fe, Co, Cu) aluminylene complexes is reported. DFT and ab<b> </b>initio calculations have been used to provide detailed insight into the metal–metal bond. The σ-donation and π-backdonation properties of the aluminylene ligand are evaluated via NBO and ETS-NOCV calculations. These calculations reveal that these ligands are strong σ-donors but also competent π-acceptors. These properties are not fixed but vary in response to the nature of the transition metal centre, suggesting that aluminylene fragments can modulate their bonding to accommodate both electron-rich and electron-poor transition metals. Ab initio<b> </b>DLPNO-CCSD(T) calculations show that dispersion plays an important role in stabilising these complexes. Both short-range and long-range dispersion interactions are identified. These results will likely inform the design of next-generation catalysts based on aluminium metalloligands. </i>

Characterizations of Novel Binuclear Transition Metal Polynitrogen Compounds: M2(N5)4 (M=Co, Rh and Ir)

2014 ◽  
Vol 924 ◽  
pp. 233-252 ◽  
Author(s):  
Li Hong Tang ◽  
Hui Bin Guo ◽  
Qian Shu Li ◽  
Jin Hui Peng ◽  
Jun Jie Gu ◽  
...  
Keyword(s):  
Transition Metal ◽  
Nbo Analysis ◽  
High Order ◽  
Multiple Bonds ◽  
Dissociation Energies ◽  
Nucleus Independent Chemical Shift ◽  
Metal Atoms ◽  
Metal Metal ◽  
Natural Bonding Orbital ◽  
Polynitrogen Compounds

Theoretical studies on a series of binuclear transition metal pentazolides M2(N5)4(M=Co, Rh and Ir) predict Paddlewheel-type structures with very short metal-metal distances suggesting high-order metal-metal multiple bonds. Natural Bonding Orbital (NBO) analysis have indicated that the bonding between the metal atom and the five-membered ring is predominantly ionic for each M2(N5)4species, and a high-order metal-metal multiple bonding exists between the two metal atoms, in addition, the presence of the delocalized π orbital plays an important role in the stabilization of this metal-polynitrogen species. Nucleus independent chemical shift (NICS) values confirm that the planar N5exhibits aromaticity in these M2(N5)4species. The values of NICS(0.0), NICS(0.5) and NICS(1.0) for Co2(N5)4are larger than those of the other two M2(N5)4species (M=Rh and Ir), with the order of Co2(N5)4>Rh2(N5)4>Ir2(N5)4. The dissociation energies into Mononuclear Fragments for M2(N5)4(M=Co, Rh and Ir) are predicted to be 82.9 (85.7), 139.9 (113.2), and 155.1 (149.7) kcal/mol, respectively. However, the dissociation energies for the loss of one pentazolato group from the M2(N5)4analysis have indicated that the Co2(N5)4is relatively higher at ~40 kcal/mol. Thermochemistry suggests Co2(N5)4to be a viable species.

Assessing cathode property prediction via exchange-correlation functionals with and without long-range dispersion corrections

2021 ◽  
Author(s):  
Olivia Long ◽  
Gopalakrishnan Sai Gautam ◽  
Emily Ann Carter
Keyword(s):  
Transition Metal ◽  
Metal Oxides ◽  
Lithium Ion Batteries ◽  
Long Range ◽  
Transition Metal Oxides ◽  
Lithium Ion ◽  
Band Gaps ◽  
Property Prediction ◽  
Exchange Correlation

We benchmark calculated interlayer spacings, average topotactic voltages, thermodynamic stabilities, and band gaps in layered lithium transition-metal oxides (TMOs) and their de-lithiated counterparts, which are used in lithium-ion batteries as...

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