1. Volume 1, Issue 6, Pages 902-920 (December 2016)
Cationic Two-Coordinate Complexes of Pd(I) and Pt(I) Have Longer Metal-Ligand Bonds Than Their Neutral Counterparts 
Morgan C. MacInnis, Jessica C. DeMott, Eva M. Zolnhofer, Jia Zhou, Karsten Meyer, Russell P. Hughes, Oleg V. Ozerov 
Chem 
Volume 1, Issue 6, Pages (December 2016)
DOI: /j.chempr
Copyright © 2016 Elsevier Inc. Terms and Conditions

2. Chem 2016 1, DOI: ( /j.chempr )
Copyright © 2016 Elsevier Inc. Terms and Conditions

3. Figure 1
POV-Ray Renditions of Oak Ridge Thermal-Ellipsoid Plots of Complexes 4 and 11
[(tBu3P)2Pt][HCB11Cl11] (4, left) and [(tBu3P)2Pd(NCMe)][HCB11Cl11] (11, right). The structure of 3 is isomorphous to 4 and is not shown separately. Thermal ellipsoids are displayed at the 50% level. Hydrogen atoms and a co-crystallized molecule of acetonitrile in the structure of 11 are omitted for clarity. Selected bond length (Å) and angle (°) for 3: Pd-P1, (5); P1-Pd-P2, 180. Selected bond length (Å) and angle (°) for 4: Pd-P1, (6); P1-Pd-P2, 180. Selected bond lengths (Å) and angles (°) for 11: Pd-P (9); Pd-P (10); Pd-N (15); P1-Pd-P (15); N1-Pd-P (5); N1-Pd-P (5). Persistence of Vision Ray Tracer (POV-Ray) is available at ORTEP plots were created with ORTEP-3 for Windows.47
Chem 2016 1, DOI: ( /j.chempr )
Copyright © 2016 Elsevier Inc. Terms and Conditions

4. Figure 2
Depiction of Calculated Singly Occupied MOs for the Cations of 3, 4, and 11
Cation of 3 (left), cation of 4 (center), and cation of 11 (right). Isovalue = Hydrogen atoms are omitted for clarity.
Chem 2016 1, DOI: ( /j.chempr )
Copyright © 2016 Elsevier Inc. Terms and Conditions

5. Figure 3 Calculated Spin-Density Plots for the Cations of 3, 4, and 11
Cation of 3 (left), cation of 4 (center), and cation of 11 (right). Isovalue = Hydrogen atoms are omitted for clarity.
Chem 2016 1, DOI: ( /j.chempr )
Copyright © 2016 Elsevier Inc. Terms and Conditions

6. Figure 4 Generalized Representation of Molecules under Study
(A) Coordinate and labeling system used in the EDA-NOCV analysis.
(B) Interaction between the σg L2 combination and Pt(6s).
(C) Interaction between one of the orthogonal πg ligand acceptor combinations and Pt(5dxz).
Chem 2016 1, DOI: ( /j.chempr )
Copyright © 2016 Elsevier Inc. Terms and Conditions

7. Figure 5
Calculated Energy Levels at the B3LYP-D3/TZ2P/ZORA Level for the Pt(6s) and Pt(5dxz) Orbitals in Pt0 and Pt+ with the L2, σg, and πg Combinations
Chem 2016 1, DOI: ( /j.chempr )
Copyright © 2016 Elsevier Inc. Terms and Conditions

8. Figure 6
NOCV Contributions to Eorb for [Pt(PH3)2] and the Resulting Deformation Densities, Eigenvalues, and Energies Associated with Each
Left: the NOCV orbitals are the antibonding version of each pair for better visual separation of their components.
Middle: for deformation densities, the sense of electron “flow” is from red to blue, allowing the donor and acceptor components to be visualized.
Right: eigenvalues are in italics, and energies are underlined.
Chem 2016 1, DOI: ( /j.chempr )
Copyright © 2016 Elsevier Inc. Terms and Conditions

9. Figure 7 Energy versus Pt-P Distance Plots for [Pt(PH3)2]0/+
(A) Plots of Eint (blue), Esteric (red), and Eorb (green) against the Pt–P distance for [Pt(PH3)2]0/+ redox pairs.
(B) Plots of Eint (blue), EPauli (black), and Eestat (purple) against the Pt–P distance for [Pt(PH3)2]0/+ redox pairs with relaxed PH3 geometries.
(C) Plots of Eint (blue), NOCVσ-donor stabilization (black), and NOCVπ-acceptor stabilization (red) against the Pt–P distance for [Pt(PH3)2]0/+ redox pairs with relaxed PH3 geometries.
Data points shown as squares correspond to [Pt(PH3)2]0 and circles to [Pt(PH3)2]+. Filled squares and solid lines or filled circles and dashed lines correspond to structurally relaxed PH3 ligands; open squares or circles and dotted lines refer to frozen PH3 ligand geometries. The lowest-energy values of Eint are highlighted in orange. The range of values corresponding to the equilibrium reduced and oxidized forms is highlighted in orange.
Chem 2016 1, DOI: ( /j.chempr )
Copyright © 2016 Elsevier Inc. Terms and Conditions

10. Figure 8 Energy versus Pt-P Distance Plots for [Pt(PF3)2]0/+
(A) Plots of Eint (blue), Esteric (red), and Eorb (green) against the Pt–P distance for [Pt(PF3)2]0/+ redox pairs with relaxed PF3 geometries.
(B) Plots of Eint (blue), EPauli (black), and Eestat (purple) against the Pt–P distance for [Pt(PF3)2]0/+ redox pairs with relaxed PF3 geometries.
(C) Plots of Eint (blue), NOCVσ-donor (black), and NOCVπ-acceptor (red) against the Pt–P distance for [Pt(PF3)2]0/+ redox pairs with relaxed PF3 geometries.
Data points shown as squares with solid lines correspond to [Pt(PF3)2]0, and circles with dashed lines correspond to [Pt(PF3)2]+. The lowest-energy values of Eint are highlighted in orange. The range of values corresponding to the equilibrium reduced and oxidized forms is highlighted in orange.
Chem 2016 1, DOI: ( /j.chempr )
Copyright © 2016 Elsevier Inc. Terms and Conditions

11. Figure 9 Energy versus Pt-N Distance Plots for [Pt(NH3)2]0/+
(A) Plots of Eint (blue), Esteric (red), and Eorb (green) against the Pt–N distance for [Pt(NH3)2]0/+ redox pairs with relaxed NH3 geometries.
(B) Plots of Eint (blue), EPauli (black), and Eestat (purple) against the Pt–N distance for [Pt(NH3)2]0/+ redox pairs with relaxed NH3 geometries.
(C) Plots of Eint (blue), NOCVσ-donor (black), and NOCVπ-acceptor (red) against the Pt–N distance for [Pt(NH3)2]0/+ redox pairs with relaxed NH3 geometries.
Data points shown as squares with solid lines correspond to [Pt(NH3)2]0, and circles with dashed lines correspond to [Pt(NH3)2]+. The lowest-energy values of Eint are highlighted in orange. The range of values corresponding to the equilibrium reduced and oxidized forms is highlighted in orange.
Chem 2016 1, DOI: ( /j.chempr )
Copyright © 2016 Elsevier Inc. Terms and Conditions

12. Scheme 1 Synthesis and Reactivity of Pd(I) and Pt(I) Complexes
Chem 2016 1, DOI: ( /j.chempr )
Copyright © 2016 Elsevier Inc. Terms and Conditions

13. Scheme 2
Calculated Energies for Phosphine Dissociation from 2 or the Cation of 4
Chem 2016 1, DOI: ( /j.chempr )
Copyright © 2016 Elsevier Inc. Terms and Conditions