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Oronzo Sciacovelli - One of the best experts on this subject based on the ideXlab platform.
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multinuclear and dynamic nmr study of trans pt cl phcy2 2 pcy2 pt cl phcy2 3 bf4 pt cl phcy2 3 cl trans pt cl phcy2 2 p s cy2 and trans pt cl phcy2 2 p o cy2 influence of intramolecular po h p and cl h p interactions on restricted rotation about pt p bond x ray structure of trans pt cl phcy2 2 p o cy2
Inorganic Chemistry, 2005Co-Authors: Piero Mastrorilli, Cosimo Francesco Nobile, Mario Latronico, Vito Gallo, Ulli Englert, Francesco Paolo Fanizzi, Oronzo SciacovelliAbstract:Dynamic NMR experiments on trans-[Pt(Cl)(PHCy2)2{P(X)Cy2}]z where X is a lone pair (1, z = 0), H (2, z = +1), S (3, z = 0), or O (4, z = 0) show that the rotation around the P(X)−Pt bond is hindered for all molecules studied, with ΔG⧧ ranging from 8.2 to 11.0 kcal/mol. The highest value of the series was calculated for trans-[Pt(Cl)(PHCy2)2{P(O)Cy2}] (4) where intramolecular PO···H−P interactions act as a molecular brake at room temperature. Single-crystal X-ray diffraction confirms the presence of both intra and intermolecular PO···H interactions in solid 4. In the case of [Pt(Cl)(PHCy2)3]Cl, multinuclear NMR analysis indicates the presence of a P−H···Cl- interaction in aromatic or halogenated solvents which could have also a minor effect on the Rotational Barrier around the P(X)−Pt bond.
Piero Mastrorilli - One of the best experts on this subject based on the ideXlab platform.
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multinuclear and dynamic nmr study of trans pt cl phcy2 2 pcy2 pt cl phcy2 3 bf4 pt cl phcy2 3 cl trans pt cl phcy2 2 p s cy2 and trans pt cl phcy2 2 p o cy2 influence of intramolecular po h p and cl h p interactions on restricted rotation about pt p bond x ray structure of trans pt cl phcy2 2 p o cy2
Inorganic Chemistry, 2005Co-Authors: Piero Mastrorilli, Cosimo Francesco Nobile, Mario Latronico, Vito Gallo, Ulli Englert, Francesco Paolo Fanizzi, Oronzo SciacovelliAbstract:Dynamic NMR experiments on trans-[Pt(Cl)(PHCy2)2{P(X)Cy2}]z where X is a lone pair (1, z = 0), H (2, z = +1), S (3, z = 0), or O (4, z = 0) show that the rotation around the P(X)−Pt bond is hindered for all molecules studied, with ΔG⧧ ranging from 8.2 to 11.0 kcal/mol. The highest value of the series was calculated for trans-[Pt(Cl)(PHCy2)2{P(O)Cy2}] (4) where intramolecular PO···H−P interactions act as a molecular brake at room temperature. Single-crystal X-ray diffraction confirms the presence of both intra and intermolecular PO···H interactions in solid 4. In the case of [Pt(Cl)(PHCy2)3]Cl, multinuclear NMR analysis indicates the presence of a P−H···Cl- interaction in aromatic or halogenated solvents which could have also a minor effect on the Rotational Barrier around the P(X)−Pt bond.
David A Mazziotti - One of the best experts on this subject based on the ideXlab platform.
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strongly correlated Barriers to rotation from parametric two electron reduced density matrix methods in application to the isomerization of diazene
Journal of Chemical Physics, 2012Co-Authors: Andrew M Sand, Christine A Schwerdtfeger, David A MazziottiAbstract:Recently, parameterization of the two-electron reduced density matrix (2-RDM) has made possible the determination of electronic energies with greater accuracy and lower cost than traditional electron-pair theories including coupled cluster with single and double excitations [D. A. Mazziotti, Phys. Rev. Lett. 101, 253002 (2008)]. We examine the method's performance for strongly correlated Barriers to rotation; in particular, we study two distinct pathways in the isomerization of diazene (N2H2) from cis to trans: (i) a strongly correlated Rotational pathway and (ii) a moderately correlated inversion pathway. While single reference wavefunction methods predict that the Rotational Barrier is higher than the inversional Barrier, the parametric 2-RDM method predicts that the Rotational Barrier is lower than the inversional Barrier by 3.1 kcal/mol in the extrapolated basis set limit. The parametric 2-RDM results are in agreement with those from multireference methods including multireference perturbation theory ...
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strongly correlated Barriers to rotation from parametric two electron reduced density matrix methods in application to the isomerization of diazene
Journal of Chemical Physics, 2012Co-Authors: Andrew M Sand, Christine A Schwerdtfeger, David A MazziottiAbstract:Recently, parameterization of the two-electron reduced density matrix (2-RDM) has made possible the determination of electronic energies with greater accuracy and lower cost than traditional electron-pair theories including coupled cluster with single and double excitations [D. A. Mazziotti, Phys. Rev. Lett. 101, 253002 (2008)]. We examine the method's performance for strongly correlated Barriers to rotation; in particular, we study two distinct pathways in the isomerization of diazene (N2H2) from cis to trans: (i) a strongly correlated Rotational pathway and (ii) a moderately correlated inversion pathway. While single reference wavefunction methods predict that the Rotational Barrier is higher than the inversional Barrier, the parametric 2-RDM method predicts that the Rotational Barrier is lower than the inversional Barrier by 3.1 kcal/mol in the extrapolated basis set limit. The parametric 2-RDM results are in agreement with those from multireference methods including multireference perturbation theory and the solution to the anti-Hermitian contracted Schrodinger equation. We report energies, optimized structures, and natural orbital occupation numbers for three diazene minima and two transition states.
Francesco Paolo Fanizzi - One of the best experts on this subject based on the ideXlab platform.
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multinuclear and dynamic nmr study of trans pt cl phcy2 2 pcy2 pt cl phcy2 3 bf4 pt cl phcy2 3 cl trans pt cl phcy2 2 p s cy2 and trans pt cl phcy2 2 p o cy2 influence of intramolecular po h p and cl h p interactions on restricted rotation about pt p bond x ray structure of trans pt cl phcy2 2 p o cy2
Inorganic Chemistry, 2005Co-Authors: Piero Mastrorilli, Cosimo Francesco Nobile, Mario Latronico, Vito Gallo, Ulli Englert, Francesco Paolo Fanizzi, Oronzo SciacovelliAbstract:Dynamic NMR experiments on trans-[Pt(Cl)(PHCy2)2{P(X)Cy2}]z where X is a lone pair (1, z = 0), H (2, z = +1), S (3, z = 0), or O (4, z = 0) show that the rotation around the P(X)−Pt bond is hindered for all molecules studied, with ΔG⧧ ranging from 8.2 to 11.0 kcal/mol. The highest value of the series was calculated for trans-[Pt(Cl)(PHCy2)2{P(O)Cy2}] (4) where intramolecular PO···H−P interactions act as a molecular brake at room temperature. Single-crystal X-ray diffraction confirms the presence of both intra and intermolecular PO···H interactions in solid 4. In the case of [Pt(Cl)(PHCy2)3]Cl, multinuclear NMR analysis indicates the presence of a P−H···Cl- interaction in aromatic or halogenated solvents which could have also a minor effect on the Rotational Barrier around the P(X)−Pt bond.
Cosimo Francesco Nobile - One of the best experts on this subject based on the ideXlab platform.
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multinuclear and dynamic nmr study of trans pt cl phcy2 2 pcy2 pt cl phcy2 3 bf4 pt cl phcy2 3 cl trans pt cl phcy2 2 p s cy2 and trans pt cl phcy2 2 p o cy2 influence of intramolecular po h p and cl h p interactions on restricted rotation about pt p bond x ray structure of trans pt cl phcy2 2 p o cy2
Inorganic Chemistry, 2005Co-Authors: Piero Mastrorilli, Cosimo Francesco Nobile, Mario Latronico, Vito Gallo, Ulli Englert, Francesco Paolo Fanizzi, Oronzo SciacovelliAbstract:Dynamic NMR experiments on trans-[Pt(Cl)(PHCy2)2{P(X)Cy2}]z where X is a lone pair (1, z = 0), H (2, z = +1), S (3, z = 0), or O (4, z = 0) show that the rotation around the P(X)−Pt bond is hindered for all molecules studied, with ΔG⧧ ranging from 8.2 to 11.0 kcal/mol. The highest value of the series was calculated for trans-[Pt(Cl)(PHCy2)2{P(O)Cy2}] (4) where intramolecular PO···H−P interactions act as a molecular brake at room temperature. Single-crystal X-ray diffraction confirms the presence of both intra and intermolecular PO···H interactions in solid 4. In the case of [Pt(Cl)(PHCy2)3]Cl, multinuclear NMR analysis indicates the presence of a P−H···Cl- interaction in aromatic or halogenated solvents which could have also a minor effect on the Rotational Barrier around the P(X)−Pt bond.
