Gold(I)-Mediated Rearrangement of 1,2-Diphenylhydrazine to Semidines

Xia, Aibing; James, and Alan J.; Sharp, Paul R.

doi:10.1021/om980763j

Cited by 12 publications

(6 citation statements)

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“…In 3, the four-coordinated N(1) atom is surrounded by three gold atoms and the dansyl group in the form of a distorted tetrahedron. The Au\N(1) distances (2.080(7)-2.094(7) Å) are similar to those found in related [(AuPPh 3 ) 3 (μ 3 -NR)] + [16][17][18][19] and are longer than those in 2. The Au\N(1)\Au angles (94.0(3)-97.8(3)°) are smaller than 109.5°expected for a regular tetrahedron.…”

supporting

confidence: 72%

“…This affinity can be increased if more than one gold atom is attached to the nitrogen atom. Schmidbaur, Sharp, and Rees have previously reported the synthesis of di-, tri-, as well as tetra-nuclear gold(I) amido and imido complexes [15][16][17][18][19][20]. However, to the best of our knowledge, the photoluminescence properties of these kinds of complexes have not been studied.…”

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confidence: 99%

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Mono-, di-, and tri-nuclear gold(I) complexes with dansyl moiety: Synthesis, characterization, and photophysical properties

Chao

et al. 2011

Inorganic Chemistry Communications

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confidence: 72%

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confidence: 99%

Mono-, di-, and tri-nuclear gold(I) complexes with dansyl moiety: Synthesis, characterization, and photophysical properties

Chao

et al. 2011

Inorganic Chemistry Communications

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“…The crystal structure of the former has been determined. Both species can be obtained independently by reaction of the gold oxo complex with the corresponding ortho or para-semidine[143].…”

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confidence: 99%

Gold–Gold Interactions

Crespo

2008

Modern Supramolecular Gold Chemistry

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This chapter focuses mainly on closed shell gold(I) atoms which are found to feel attraction among themselves. This attraction is able to modify expected geometries or support one-, two-or three-dimensional arrays and also leads to interesting properties. Closed shell metal cations are expected to repel each other. Nevertheless, an important number of examples containing [d 8 -d 10 -s 2 ] interactions are known. Particularly strong evidence has been accumulated on the attraction between two or more d 10 shells. In the case of gold(I) such attraction between two or more monovalent gold(I) ions in compounds has been observed structurally for a long time. In these situations the gold centers approach each other to a distance of between 2.7 and 3.3 Å. This range includes the distance between gold atoms in gold metal and approaches, or even overlaps with the range of distances found in the few real Au-Au single bonds. Schmidbaur coined the name aurophilic attraction in 1990 and defined it as the unprecedented affinity between gold atoms even with closed-shell electronic configurations and equivalent electrical charges [1]. Since that moment, aurophilicity has become one of the hot topics in gold chemistry, at first with the aim of understanding such interaction, more recently because of the observation that it may play an important role in interesting properties, thus understanding and modulating aurophilic interactions could help to govern these properties, which include the optical behavior. Although different origins are possible for the luminescent emissions of coordination complexes, such as intraligand transitions (ILT), ligand to metal or metal to ligand charge transfer transitions (LMCT, MLCT) and metal centered (MCT) transitions, in many luminescent gold complexes the emissions have been related to the presence of aurophilic interactions.Information about aurophilicity and chemical situations in which it is observed may be found in different works that may be classified as those which analyse closed shell interactions in general [2], those focused on aurophilicity [1,3], and others which analyze the role of these interactions in coordination [4] and organometallic gold Modern Supramolecular Gold Chemistry: Gold-Metal Interactions and Applications. Edited by Antonio Laguna

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“…The type of complex isolated depends on the hydrazine substitution. With unsubstituted hydrazine, the first group 11 dinitrogen complexes [(LAu) 6 (μ-N 2 )] 2+ were obtained, − while with substituted hydrazines either the trimetallic hydrazido complexes, − [(LAu) 3 (μ-NNR 2 )] + or rearranged semidine complexes [(LAu) 3 (μ-NC 6 H 4 NHPh)] + , were isolated. Similar exchange reactions with the platinum hydroxo complexes [L 2 Pt(μ-OH)] 2 2+ (L 2 = a bidentate diphosphine) and hydrazine yielded the dimetallic dihydrazido complexes [L 2 Pt(μ-NHNH 2 )] 2 2+ .…”

Section: Introductionmentioning

confidence: 99%

Platinum(II) Hydrazido Complexes

Xia

Sharp

2001

Inorg. Chem.

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Reaction of 1,2-dimethylhydrazine with the platinum hydroxo complex [(dppp)Pt(mu-OH)](2)(BF(4))(2) gives the bridging 1,2-dimethylhydrazido(-2) product [(dppp)(2)Pt(2)(mu-eta(2):eta(2)-MeNNMe)](BF(4))(2) 1. Crystals of 1.CH(2)Cl(2) from CH(2)Cl(2)/Et(2)O are monoclinic (C/2) with a = 19.690(1), b = 18.886(1), c = 17.170 (1) A, and beta = 92.111(1) degrees. Treatment of [(dppp)Pt(mu-OH)](2)(OTf)(2) with 1,1-dimethylhydrazine gives [(dppp)(2)Pt(2)(mu-OH)(mu-NHNMe(2))](OTf)(2) 2. Crystals of 2.CH(2)Cl(2) from CH(2)Cl(2)/Et(2)O are triclinic (P-1) with a = 12.910 (3), b = 13.927(3), c = 17.5872 (3) A, alpha = 87.121(3), beta = 89.997(4), and gamma = 84.728(3) degrees. Reaction of [(dppp)Pt(mu-OH)](2)(OTf)(2) with 1 equiv of phenylhydrazine in CH(2)Cl(2) gives [(dppp)(2)Pt(2)(mu-OH)(mu-NHNHPh)](OTf)(2) 3. Two equivalents of phenylhydrazine with [(dppp)Pt(mu-OH)](2)(X)(2) gives [(dppp)Pt(mu-NHNHPh)](2)(X)(2) 4 (X = BF(4), OTf). Crystals of 3.ClCH(2)CH(2)Cl from ClCH(2)CH(2)Cl/(i)()Pr(2)O are monoclinic (P2(1)/n) with a = 20.990(2), b = 13.098(1), c = 25.773 (2) A, and beta = 112.944(2) degrees. Crystals of 4(X = BF(4)).ClCH(2)CH(2)Cl(.)()2((t)()BuOMe) from ClCH(2)CH(2)Cl/(t)()BuOMe are monoclinic (C2/m) with a = 30.508(1), b = 15.203(1), c = 19.049 (1) A, and beta = 118.505(2) degrees.

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Gold(I)-Mediated Rearrangement of 1,2-Diphenylhydrazine to Semidines

Cited by 12 publications

References 13 publications

Mono-, di-, and tri-nuclear gold(I) complexes with dansyl moiety: Synthesis, characterization, and photophysical properties

Mono-, di-, and tri-nuclear gold(I) complexes with dansyl moiety: Synthesis, characterization, and photophysical properties

Gold–Gold Interactions

Platinum(II) Hydrazido Complexes

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