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Comments on Inorganic Chemistry
A Journal of Critical Discussion of the Current Literature
Volume 38, 2018 - Issue 1
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All That Glitters Is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d10 Metal Centers—A Tribute to Al Cotton on the Tenth Anniversary of His Passing

Brooke M. OttenDepartment of Chemistry, University of North Texas, Denton, Texas, USAORCID Iconhttp://orcid.org/0000-0002-7612-665XView further author information
ORCID Icon,
Kortney M. MelançonDepartment of Chemistry, University of North Texas, Denton, Texas, USAORCID Iconhttp://orcid.org/0000-0002-2505-6989View further author information
ORCID Icon &
Mohammad A. OmaryDepartment of Chemistry, University of North Texas, Denton, Texas, USACorrespondence[email protected]
ORCID Iconhttp://orcid.org/0000-0002-3247-3449View further author information
ORCID Icon
Pages 1-35 | Published online: 18 Jun 2018

Figures & data

Figure 1 Structures of AuAg[MTP(R)]2 (A) and AuCu[MTP(R)]2 (B) models (R = Ph or H) and the Pt2(PCP)2 model (C).

Figure 1 Structures of AuAg[MTP(R)]2 (A) and AuCu[MTP(R)]2 (B) models (R = Ph or H) and the Pt2(PCP)2 model (C).

Table 1 Selected bond lengths (Å) and angles (°) for the coordination geometry in the Ag2[MTP(Ph)]2 and Au2[MTP(Ph)]2 complexes

Figure 2 Calculated geometry of the Cu2[MTP(Ph)]2 complex with the C-Cu-S angles (°) shown.

Figure 2 Calculated geometry of the Cu2[MTP(Ph)]2 complex with the C-Cu-S angles (°) shown.

Figure 3 Molecular orbital contours of the Au2[MTP(Ph)]2 complex (isodensity = 0.03 a.u.). Orbital notation is given to describe relative energy (e.g., HOMO–6 = the orbital that lies sixth below the highest occupied molecular orbital).

Figure 3 Molecular orbital contours of the Au2[MTP(Ph)]2 complex (isodensity = 0.03 a.u.). Orbital notation is given to describe relative energy (e.g., HOMO–6 = the orbital that lies sixth below the highest occupied molecular orbital).

Table 2 Kohn-Sham orbital contribution analysis for [Au(MTP(H))]2

Table 3 Kohn-Sham orbital analysis for [Ag(MTP(H))]2

Table 4 Kohn-Sham orbital analysis for [Cu(MTP(H))]2

Table 5 Atomic energy level splitting for Au(I), Ag(I), and Cu(I) reported in cm−1 units for the singlet and triplet excited states, including the weighted average of the spin-orbit microstates of the latter

Table 6 Natural bond order orbital (NBO) analysis for M2[MTP(H)]2 complexes

Figure 4 Molecular orbital contours of the Ag2[MTP(H)]2 complex (isodensity = 0.03 a.u.).

Figure 4 Molecular orbital contours of the Ag2[MTP(H)]2 complex (isodensity = 0.03 a.u.).

Figure 5 Molecular orbital contours of the Cu2[MTP(H)]2 complex (isodensity = 0.03 a.u.).

Figure 5 Molecular orbital contours of the Cu2[MTP(H)]2 complex (isodensity = 0.03 a.u.).

Figure 6 Selected total density contours for the Au2[MTP(Ph)]2 complex (isodensity value labeled in each as “Isovalue” in a.u. units).

Figure 6 Selected total density contours for the Au2[MTP(Ph)]2 complex (isodensity value labeled in each as “Isovalue” in a.u. units).

Table 7 Selected bond lengths (Å) and angles (°) for Au2 complexes at M06/CEP-31g(d)

Table 8 Natural bond order analysis for MM[MTP(Ph)]2

Figure 7 Illustration of the donor-acceptor interaction in Au2[MTP(H)]2 by superimposing the Au 5d orbital with the Au’ 6p orbital from NBO population analysis (isodensity = 0.03 a.u.).

Figure 7 Illustration of the donor-acceptor interaction in Au2[MTP(H)]2 by superimposing the Au 5d orbital with the Au’ 6p orbital from NBO population analysis (isodensity = 0.03 a.u.).

Figure 8 Molecular orbital contours of the Pt2(PCP)2 model (isodensity = 0.03 a.u.).

Figure 8 Molecular orbital contours of the Pt2(PCP)2 model (isodensity = 0.03 a.u.).

Table 9 Selected bond lengths (Å) and angles (°) for AuAg[MTP(R)]2

Table 10 Selected bond lengths (Å) and angles (°) for AuCu[MTP(R)]2

Figure 9 Calculated geometry of AuCu[MTP(Ph)]2 complex with the C-Cu-S angles (°) shown.

Figure 9 Calculated geometry of AuCu[MTP(Ph)]2 complex with the C-Cu-S angles (°) shown.

Figure 10 Calculated geometry of AuCu[MTP(Ph)]2 complex with the C-Cu-S angles (°) shown.

Figure 10 Calculated geometry of AuCu[MTP(Ph)]2 complex with the C-Cu-S angles (°) shown.

Figure 11 Selected Hartree-Fock molecular orbital contours of [AuAg(MTP)2] from MP2 calculations (isodensity = 0.03 a.u.).

Figure 11 Selected Hartree-Fock molecular orbital contours of [AuAg(MTP)2] from MP2 calculations (isodensity = 0.03 a.u.).

Figure 12 Total density contours for Au2[MTP(H)]2, AuAg[MTP(H)]2, and Ag2[MTP(H)]2 (isodensity value labeled in each as “Isovalue” in a.u. units).

Figure 12 Total density contours for Au2[MTP(H)]2, AuAg[MTP(H)]2, and Ag2[MTP(H)]2 (isodensity value labeled in each as “Isovalue” in a.u. units).

Figure 13 Selected Hartree-Fock molecular orbital contours of AuCu[MTP(H)]2 from MP2 calculations (isodensity = 0.03 a.u.).

Figure 13 Selected Hartree-Fock molecular orbital contours of AuCu[MTP(H)]2 from MP2 calculations (isodensity = 0.03 a.u.).

Figure 14 Total density contours for Au2[MTP(H)]2, AuCu[MTP(H)]2, and Cu2[MTP(H)]2 (isodensity value labeled in each as “Isovalue” in a.u. units).

Figure 14 Total density contours for Au2[MTP(H)]2, AuCu[MTP(H)]2, and Cu2[MTP(H)]2 (isodensity value labeled in each as “Isovalue” in a.u. units).

Table 11 Natural bond order analysis for AuAg[MTP(Ph)]2 and AuCu[MTP(Ph)]2

Figure 15 Illustration of the donor-acceptor interaction in AuCu[MTP(H)]2 from the Au 5d donor orbital (left) to the Cu 6p orbital (middle) to form the superimposed NBO orbital (right) (isodensity = 0.03 a.u.).

Figure 15 Illustration of the donor-acceptor interaction in AuCu[MTP(H)]2 from the Au 5d donor orbital (left) to the Cu 6p orbital (middle) to form the superimposed NBO orbital (right) (isodensity = 0.03 a.u.).

Figure 16 Calculated normalized absorption spectra of Au2[MTP(Ph)]2, Cu2[MTP(Ph)]2, and Ag2[MTP(Ph)]2 with the highest orbital contribution from Au2[MTP(Ph)]2 (isodensity = 0.03 a.u. for the orbital contours depicted in the inset for the major transition).

Figure 16 Calculated normalized absorption spectra of Au2[MTP(Ph)]2, Cu2[MTP(Ph)]2, and Ag2[MTP(Ph)]2 with the highest orbital contribution from Au2[MTP(Ph)]2 (isodensity = 0.03 a.u. for the orbital contours depicted in the inset for the major transition).

Figure 17 Calculated normalized absorption spectra of Au2[MTP(Ph)]2, Ag2[MTP(Ph)]2 and AuAg[MTP(Ph)]2 (isodensity = 0.03 a.u. for the orbital contours depicted in the inset for the major transition in the AuAg complex).

Figure 17 Calculated normalized absorption spectra of Au2[MTP(Ph)]2, Ag2[MTP(Ph)]2 and AuAg[MTP(Ph)]2 (isodensity = 0.03 a.u. for the orbital contours depicted in the inset for the major transition in the AuAg complex).

Figure 18 Calculated normalized absorption spectra of Au2[MTP(Ph)]2, Cu2[MTP(Ph)]2, and AuCu[MTP(Ph)]2 with the major orbital contribution for the AuCu[MTP(Ph)]2 complex (isodensity = 0.03 a.u. for the orbital contours depicted in the inset for the major transition).

Figure 18 Calculated normalized absorption spectra of Au2[MTP(Ph)]2, Cu2[MTP(Ph)]2, and AuCu[MTP(Ph)]2 with the major orbital contribution for the AuCu[MTP(Ph)]2 complex (isodensity = 0.03 a.u. for the orbital contours depicted in the inset for the major transition).

Figure 19 Selected molecular orbital contours of the Au2[MTP(Ph)]2 complex with isodensity values varied from 0.02 a.u. (top) to magnify the bonding interaction vs the 0.03 a.u. values used in and other figures.

Figure 19 Selected molecular orbital contours of the Au2[MTP(Ph)]2 complex with isodensity values varied from 0.02 a.u. (top) to magnify the bonding interaction vs the 0.03 a.u. values used in Figure 3 and other figures.

Figure 20 Molecular orbital contours of the Cu2[MTP(Ph)]2 complex that manifest a Cu-Cu bonding character upon using 0.02 a.u. isodensity value.

Figure 20 Molecular orbital contours of the Cu2[MTP(Ph)]2 complex that manifest a Cu-Cu bonding character upon using 0.02 a.u. isodensity value.

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