Catalytic Applications of Early/Late Heterobimetallic Complexes

Cooper, Benjamin G.; Napoline, J. Wesley; Thomas, Christine M.

doi:10.1080/01614940.2012.619931

Cited by 260 publications

(184 citation statements)

References 97 publications

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“…4B and SI Appendix, Table S2). This is exactly opposite to the situation in Cotton's work on M 2 (form) 2 2 species. Additional theoretical insights for 3d σ -5d σ /3d π -5d π /3d δ -5d δ bonding are addressed based on dispersive density functional theory (DFT) computations (discussed below).…”

contrasting

confidence: 46%

“….. Although the metal-metal distances are short (Cu-Cu = 2.497 (2) and Ag-Ag = 2.705(1) Å), we conclude that there is little or no direct metal-metal bonding.…”

mentioning

confidence: 96%

“…This situation is akin to that for π (n)p bonding orbitals becoming lower in energy than σ (n)p bonding orbitals in the bonding scheme of heteronuclear vs. homonuclear diatomics of main-group elements due to greater (n)p/(n)s orbital mixing in the former, as postulated in typical inorganic chemistry textbooks (42). Such influences of polar covalency are magnified in ligand-containing models of 4a, including the full {[Au 4 (μ-C 2 ,N 3 -EtIm) 4 Cu 2 (μ-3,5-(CF 3 ) 2 Pz) 2 ]} hexanuclear dimer-of-trimer model and the [Au 2 (μ-C 2 ,N 3 -EtIm) 2 Cu 2 (μ-3,5-(CF 3 ) 2 Pz) 2 ] tetranuclear cluster model of interconnected corner units (SI Appendix, Scheme S2). As a consequence, the antibonding d z2 -d z2 σ* in Cotton's M-M bonding scheme becomes a nonbonding orbital when one considers, as a second step, the interaction of this molecular orbital with the (n+1)s/p z atomic orbital of the second atom.…”

mentioning

confidence: 99%

“…Heterometallic complexes are remarkable molecules owing to their unique catalytic and optoelectronic properties (2,3). Heterometallic species involving coinage metals have received immense attention owing to their fascinating structural and photophysical properties, including polar-metallophilic interactions and stimulus-responsive luminescence (3)(4)(5)(6)(7)(8)(9).…”

mentioning

confidence: 99%

“…The Cu-Au bonding formalism in the full hexanuclear dimer-of-trimer model of 4a involves initial metal-metal bonding within a monomer-of-trimer that leads to equally occupied bonding and antibonding orbitals with a formal 0 bond order, as a first step. Upon intertrimer CuAu bonding in the hexanuclear dimer-of-trimer as a second step, however, one needs to consider two factors: (i) the interaction of the two "corner units" considered hitherto for the [Au 2 (μ-C 2 ,N 3 -EtIm) 2 Cu 2 (μ-3,5-(CF 3 ) 2 Pz) 2 ] tetranuclear cluster model, which generates six Cu-Au bonding orbitals (SI Appendix , Fig. S3); and (ii) crystal field theory considerations dictate stronger intratrimer interactions for d xy and d x2-y2 orbitals as well as, albeit to a lesser extent, d z2 orbitals of the two Au(I) and one Cu(I) atoms in the trigonal-planar monomer-of-trimer model to initially form three δ bonding orbitals and three δ* antibonding orbitals.…”

mentioning

confidence: 99%

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Cupriphication of gold to sensitize d ¹⁰ –d ¹⁰ metal–metal bonds and near-unity phosphorescence quantum yields

Galassi

Ghimire

Otten

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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Outer-shell s 0 /p 0 orbital mixing with d 10 orbitals and symmetry reduction upon cupriphication of cyclic trinuclear trigonal-planar gold(I) complexes are found to sensitize ground-state Cu(I)-Au(I) covalent bonds and near-unity phosphorescence quantum yields. Heterobimetallic Au 4 Cu 2 {[Au 4 (μ-C 2 ,N 3 -EtIm) 4 Cu 2 (μ-3,5-(CF 3 ) 2 Pz) 2 ], (4a)}, Au 2 Cu {[Au 2 (μ-C 2 ,N 3 -BzIm) 2 Cu(μ-3,5-(CF 3 ) 2 Pz)], (1) and [Au 2 (μ-C 2 , N 3 -MeIm) 2 Cu(μ-3,5-(CF 3 ) 2 Pz)], (3a)}, AuCu 2 {[Au(μ-C 2 ,N 3 -MeIm)Cu 2 (μ-3,5-(CF 3 ) 2 Pz) 2 ], (3b) and [Au(μ-C 2 ,N 3 -EtIm)Cu 2 (μ-3,5-(CF 3 ) 2 Pz) 2 ], (4b)} and stacked Au 3 /Cu 3 {[Au(μ-C 2 ,N 3 -BzIm)] 3 [Cu(μ-3,5-(CF 3 ) 2 Pz)] 3 , (2)} form upon reacting Au 3 {[Au(μ-C 2 ,N 3 -(N-R)Im)] 3 ((N-R)Im = imidazolate; R = benzyl/methyl/ethyl = BzIm/MeIm/EtIm)} with Cu 3 {[Cu(μ-3,5-(CF 3 ) 2 Pz)] 3 (3,5-(CF 3 ) 2 Pz = 3,5-bis(trifluoromethyl)pyrazolate)}. The crystal structures of 1 and 3a reveal stair-step infinite chains whereby adjacent dimer-of-trimer units are noncovalently packed via two Au(I)⋯Cu(I) metallophilic interactions, whereas 4a exhibits a hexanuclear cluster structure wherein two monomer-of-trimer units are linked by a genuine d 10 -d 10 polar-covalent bond with ligandunassisted Cu(I)-Au(I) distances of 2.8750(8) Å each-the shortest such an intermolecular distance ever reported between any two d 10 centers so as to deem it a "metal-metal bond" vis-à-vis "metallophilic interaction." Density-functional calculations estimate 35-43 kcal/mol binding energy, akin to typical M-M single-bond energies. Congruently, FTIR spectra of 4a show multiple far-IR bands within 65-200 cm −1 , assignable to v Cu-Au as validated by both the Harvey-Gray method of crystallographic-distance-to-force-constant correlation and dispersive density functional theory computations. Notably, the heterobimetallic complexes herein exhibit photophysical properties that are favorable to those for their homometallic congeners, due to threefold-to-twofold symmetry reduction, resulting in cuprophilic sensitization in extinction coefficient and solid-state photoluminescence quantum yields approaching unity (Φ PL = 0.90-0.97 vs. 0-0.83 for Au 3 and Cu 3 precursors), which bodes well for potential future utilization in inorganic and/or organic LED applications. Here, we show that outer 4s/p (Cu I ) and 6s/p (Au I ) orbitals can admix with the respective valence 3d and 5d orbitals to sensitize a bona fide polar-covalent metal-metal bond between two d 10 centers manifest by two rather short, 2.8750(8) Å, Cu(I)-Au(I) bonds without any ligand-bite-size assistance. The reduced symmetry in this family of complexes is also shown to impart higher extinction coefficients and phosphorescence quantum yields than those attained by the parent homometallic precursor complexes.Heterometallic complexes are remarkable molecules owing to their unique catalytic and optoelectronic properties (2, 3). Heterometallic species involving coinage metals have received immense attention owing to their fascinating structural a...

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contrasting

confidence: 46%

“….. Although the metal-metal distances are short (Cu-Cu = 2.497 (2) and Ag-Ag = 2.705(1) Å), we conclude that there is little or no direct metal-metal bonding.…”

mentioning

confidence: 96%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Cupriphication of gold to sensitize d ¹⁰ –d ¹⁰ metal–metal bonds and near-unity phosphorescence quantum yields

Galassi

Ghimire

Otten

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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Mechanisms in Heterobimetallic Reactivity

Singer¹,

Buchard²

2022

Polar Organometallic Reagents

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Heterodinuclear Transition‐Metal Complexes: Fundamentals, Synthesis, and Applications

Koessler

Butschke

2021

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Heterodinuclear transition‐metal complexes, that is coordination compounds comprising two different transition‐metal atoms, witness growing interest. This development is driven by the incentive to find complexes, which outperform their mononuclear competitors in reactivity and selectivity. It is particularly the close proximity of the two transition‐metal atoms, which promises to promote these favorable interactions denoted as “cooperative”. Therefore, mainly dinuclear complexes with direct metal–metal bonds are discussed in this article. Since the very first report of a heterodinuclear transition‐metal complex in 1960, a repertoire of methodologies for the targeted synthesis has been established. Besides the description of this progress, the focus of the present article is on the discussion of appropriate characterization methods. Typical questions concern the nature of the metal–metal bond as well as the elucidation of mechanistic details of reactions involving the polar metal–metal bonds present in heterodinuclear complexes. Several applications are detailed, in which heterodinuclear complexes either surpass the limitations of mononuclear complexes or even exhibit so far unknown reactivity. So‐called “early–late” complexes represent the most dominant branch in this context, while also “late–late” complexes show fruitful reactivity. Herein, the focus is on transition‐metal‐containing complexes, thus ignoring main‐group elements completely.

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Catalytic Applications of Early/Late Heterobimetallic Complexes

Cited by 260 publications

References 97 publications

Cupriphication of gold to sensitize d ¹⁰ –d ¹⁰ metal–metal bonds and near-unity phosphorescence quantum yields

Cupriphication of gold to sensitize d ¹⁰ –d ¹⁰ metal–metal bonds and near-unity phosphorescence quantum yields

Mechanisms in Heterobimetallic Reactivity

Heterodinuclear Transition‐Metal Complexes: Fundamentals, Synthesis, and Applications

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Catalytic Applications of Early/Late Heterobimetallic Complexes

Cited by 260 publications

References 97 publications

Cupriphication of gold to sensitize d 10 –d 10 metal–metal bonds and near-unity phosphorescence quantum yields

Cupriphication of gold to sensitize d 10 –d 10 metal–metal bonds and near-unity phosphorescence quantum yields

Mechanisms in Heterobimetallic Reactivity

Heterodinuclear Transition‐Metal Complexes: Fundamentals, Synthesis, and Applications

Contact Info

Product

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Cupriphication of gold to sensitize d ¹⁰ –d ¹⁰ metal–metal bonds and near-unity phosphorescence quantum yields

Cupriphication of gold to sensitize d ¹⁰ –d ¹⁰ metal–metal bonds and near-unity phosphorescence quantum yields