Syntheses of organogold(1+) compounds by direct auration

Smyslova, E. I.; Perevalova, É. G.; Dyadchenko, V. P.; Grandberg, K. I.; Slovokhotov, Yu.L.; Struchkov, Yu. T.

doi:10.1016/s0022-328x(00)80137-0

Cited by 56 publications

(20 citation statements)

References 10 publications

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“…The lowest-lying isomer is the doubly h 2 c. Thus, the tetraaamino-substituted allene 5 also shows a different behavior in the binding to two AuCl compared to the allenes 3 and 4. An interesting case is that of carbon suboxide, 6, which is also predicted to have three diaurated complexes with h [56] of the neutral complex 7A C H T U N G T R E N N U N G (AuPPh 3 ) 2 + (Figure 3) except for the AuÀ Au distance, which is calculated too long compared with the X-ray data.…”

Section: Resultsmentioning

confidence: 97%

“…[60] The calculated DE int value of the carbodiphosphorane (CDP) complex 1A C H T U N G T R E N N U N G (AuCl) (À71.2 kcal mol Table 2 shows that the orbital interactions DE orb in 3- [8]. Experimental values for 1(AuCCPhNO 2 ), [25] 5A C H T U N G T R E N N U N G (AuPPh 3 ) + [17a] and 8A C H T U N G T R E N N U N G (AuCl) [56] . The breakdown of the orbital term DE orb into contributions from s and p orbitals [61] indicates that the complexes 1A C 2 a is in good agreement with the experimental results, [25] except for the theoretical Au À Au distance (3.402 ), which is much longer than the experimental value (3.143 ).…”

Section: Resultsmentioning

confidence: 99%

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Distinguishing Carbones from Allenes by Complexation to AuCl

Esterhuysen

Frenking

2011

Chemistry A European J

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Quantum chemical calculations have been performed for the dicoordinated carbon compounds C(PPh(3))(2), C(NHC(Me))(2), R(2) C=C=CR(2) (R = H, F, NMe(2)), C(3)O(2), C(CN)(2)(-) and N-methyl-substituted N-heterocyclic carbene (NHC(Me)). The geometries of the complexes in which the dicoordinated carbon molecules bind as ligands to one and two AuCl moieties have been optimized and the strength and nature of the metal-ligand interactions in the mono- and diaurated complexes were investigated by means of energy decomposition analysis. The goal of the study is to elucidate the differences in the chemical behavior between carbones, allenes and carbenes. The results show that carbones bind one and two AuCl species in η(1) fashion, whereas allenes bind them in η(2) fashion. Compounds with latent divalent carbon(0) character can coordinate in more than one way, with the dominant mode indicating the degree of carbone or allene character. The calculated structures of the mono- and diaurated tetraaminoallenes (TAAs) reveal that TAAs exhibit a chameleon-like behavior: The bonding situation in the equilibrium structure is best described as allene [(R(2)N)(2)]C=C=C[(NR(2))(2)] in which the central carbon atom is a tetravalent C(IV) species, but the reactivity suggests that TAAs should be considered as divalent C(0) compounds C{C[(NR(2))(2)]}(2), that is, as "hidden" carbones. Carbon suboxide binds one AuCl preferentially in the η(1) mode, whereas the equilibrium structures of the η(1)- and η(2)-bonded diaurated complex are energetically nearly degenerate. The doubly negatively charged isoelectronic carbone C(CN)(2)(2-) binds one and two AuCl very strongly in characteristic η(1) fashion. The N-heterocyclic carbene complex, [NHC(Me)(AuCl)], possesses a high bond dissociation energy (BDE) for the splitting off of AuCl. The diaurated NHC adduct, [NHC(Me)(AuCl)(2)], has two η(1)-bonded AuCl moieties that exhibit aurophilic attraction, which yield a moderate bond strength that might be large enough for synthesizing the complex. The BDE for the second AuCl in [NHC(Me)(AuCl)(2)] is clearly smaller than the values for the second AuCl in doubly aurated carbone complexes.

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

Distinguishing Carbones from Allenes by Complexation to AuCl

Esterhuysen

Frenking

2011

Chemistry A European J

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“…The Au-P distances are short. They lie below Au-P values found for gold-phosphine clusters Irange 2.267 (2) (Jones, 1980a;Jones & Sheldrick, 1980a,b;Muir et al, 1980;Nesmeyanov, Perevalova, Struchkov, Ant[pin, Grandberg & Dyadchenko, 1980;Riley & Davis, 1980;Schmidbaur, Mandl, Bassett, Blaschke & Zimmer-Gasser, 1981;Simon & Lauher, 1980;Smyslova, Perevalova, Dyadchenko, Grandberg, Slovokhotov & Struchkov, 1981;Solans, Miravitlles, Arrieta, Germain & Declercq, 1982) and the long distances in three-and four-coordinate Au x complexes [range 2.359(6)-2.610(9)A] (Guggenberger, 1974;Jones, 1980b,c;Jones, Sheldrick, Fugner, Gotzfried & Beck, 1981).…”

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confidence: 71%

Two crystalline phases of chlorotris(2-pyridyl)phosphinegold(I)

Lock¹,

Turner²

1987

Acta Crystallogr C

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“…Two gold atoms at a common non-arene carbon atom were soon detected also in ylidic species. No comment would be necessary here, were it not that the Au-C-Au angles are found to be smaller than the tetrahedral value [82][83][84]. Equally unexpected were the readiness of formation of triauro-oxonium, -sulfonium, and -selenonium salts, and the molecular structures of these products [76a,85-89]: in all cases, steep pyramids [E(AuL)3]+ with E = 0, S, Se, and short Au•••Au contacts were detected, and these units are further dimerized to allow for even more Au•••Au intercationic interactions.…”

Section: Single-atom Bridged Polynuclear Gold Complexesmentioning

confidence: 99%