An Unprecedented Photochemical Cis to Trans Isomerization of Dinuclear Gold(I) Bis(diphenylphosphino)ethylene Complexes

Foley, Janet B.; Bruce, Alice E.; Bruce, Mitchell R. M.

doi:10.1021/ja00142a041

Cited by 27 publications

(34 citation statements)

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“…As photolysis proceeds, this singlet decreases and the singlet at ca. 7.35 ppm, due to the trans isomer grows in. The clean conversion of cis-dpaee(AuBr)2 to trans-dpaee(AuBr)2 occurs over a period of 1.5 hr.…”

Section: Resultsmentioning

confidence: 99%

“…7'=1'== It soon became evident that a significant amount of the trans-dppee complexes formed during syntheses and recrystallization, which upon further investigation led to the discovery that a photochemical process was responsible for these transformations (eq 1). 7 Interestingly, the cis-dppee ligand is not photochemicaily reactive nor does it appear that the trans-dppee(AuX)2 complexes are photochemically reactive. Thus the experimental results suggest that the close proximity of the gold atoms is critical to the excited state reactivity.…”

Section: Resultsmentioning

confidence: 99%

“…The apparent efficiency in the photochemical isomerization of cis-dppee(AuX)= (X C, Br, I) complexes, 7 prompted measurement of quantum yields. The results of )(disappearance) studies are summarized in Table 3.…”

Section: Resultsmentioning

confidence: 99%

“…The singlet at ca. 7.66 ppm in Figure 2a is assigned to the ethylene protons on the arsine ligand. As photolysis proceeds, this singlet decreases and the singlet at ca.…”

Section: Resultsmentioning

confidence: 99%

“…1) suggests an important role for Au(I)-Au(I) bonding in the activation process. 7,8 Abbreviations. The following abbreviations are used: LL = bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,5-bis(diphenylphosphino)pentane (dpppn), 1,2-bis-(diphenylphosphino)ethylene (dppee), 1,2-bis-(diphenylarsino)ethylene (dpaee).…”

Section: Introductionmentioning

confidence: 99%

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Electronic Structure of Dinuclear Gold(I) Complexes

et al. 1999

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Cyclic voltammetry (CV) experiments on LL(AuSR*)= complexes [LL diphenylphosphinomethane (dppm), diphenylphosphinopentane (dpppn); R* = p-SCH4CH] show anodic sweeps that broaden by about 25 mV on going from the longer (dpppn) to the shorter (dppm) bidentate phosphine ligand. Changing concentrations had no effect on the shape of the waveform. The result suggests a weak intramolecular metal-metal interaction in dppm(AuSR*)= that correlates well with rate acceleration occurring in the reaction of dppm(AuSR*)=with organic disulfides. Quantum yields for cis-dppee(AuX)= [dppee 1,2-bis(diphenylphosphino)ethylene; X CI, Br, I] complexes, d>(dlsappearance), are significantly higher in complexes with a softer X ligand, a trend that correlates well with aurophilicity. This result also suggests that electronic perturbation caused by Au(I)-Au(I) interactions is important in explaining the reactivity of some dinuclear gold(I) complexes. The crystal structure for cis-dppee(Aul)= shows short intramolecular Au(I)-Au(I) interactions of 2.9526 (6) Jk, while the structure of trans-dppee(Aul)=, shows intermolecular Au(I)-Au(I) interactions of 3.2292 (9) . .T he substitution of As for P results in a ligand, cisdiphenylarsinoethylene (cis-dpaee), that is photochemically active, in contrast to the cis-dppee ligand. The complexes, cis-dpaee(AuX)=, are also photochemically active but with lower quantum yields than the cis-dppee(AuX)= complexes.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…The singlet at ca. 7.66 ppm in Figure 2a is assigned to the ethylene protons on the arsine ligand. As photolysis proceeds, this singlet decreases and the singlet at ca.…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electronic Structure of Dinuclear Gold(I) Complexes

et al. 1999

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Metallophilic Interactions in Closed-Shell Copper(I) Compounds—A Theoretical Study

2001

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Cuprophilic interactions in neutral perpendicular model dimers of the type (CH3CuX)2 (X = OH2, NH3, SH2, PH3, N2, CO, CS, CNH, CNLi) were analyzed by ab initio quantumchemical methods. The basis set superposition error for the weakly interacting CH3CuX subunits is significant and is discussed in detail. A new correlation-consistent pseudopotential valence basis set for Cu. derived at the second-order Møller-Plesset level suppresses considerably the basis set superposition error in Cu-Cu interactions compared to the standard Hartree-Fock optimized valence basis set. This allowed the first accurate predictions of cuprophilicity, which has been the subject of considerable debate in the past. The dependence of the strength of cuprophilic interactions on the nature of the ligand X was addressed. The Cu-Cu interaction increases with increasing sigma-donor and pi-acceptor capability of the ligand and is approximately one-third of the well-documented aurophilic interactions. By fitting our potential-energy data to the Hershbach-Laurie equation, we determined a relation between the Cu-Cu bond length and the Cu-Cu force constant; this is important for future studies on vibrational behaviour. The role of relativistic effects on the structure and the interaction energy is also discussed. Finally we investigated cuprophilic interactions in (CH3Cu)4 as a model species for compounds isolated and characterized by X-ray diffraction.

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