Isolation and Structural Characterization of [P(AuPPh3)5][BF4]2 via Cleavage of a P−P Bond by Cationic Gold Fragments:  Direct Evidence of the Structure of the Elusive Tetrakis[phosphineaurio(I)]phosphonium(+) Cation

Bachman, Robert E.; Schmidbaur, Hubert

doi:10.1021/ic950946n

Cited by 41 publications

(24 citation statements)

References 19 publications

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“…For P, it was predicted that C 4 v would lie below C 3 v , which in turn is preferred over T d . Such tetragonal P[(AuL) 4 ] + structures have been found with a fifth, apical gold atom by Schmidbaur et al133 and by Bachman and Schmidbaur 134. Thus the aurophilicity between the Au atoms can be strong enough to override the tendency of the central E atom to form a tetrahedron and use its sp 3 hybridized orbitals.…”

Section: Results From Theoretical Calculationsmentioning

confidence: 88%

Theoretical Chemistry of Gold

2004

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Section: Results From Theoretical Calculationsmentioning

confidence: 88%

Theoretical Chemistry of Gold

2004

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“…The first members of the series, namely the starting products for the synthesis of complexes with higher nuclearities, are synthesized by different methods, depending [95,[105][106][107][108]. As commented above, the structure of [Au 4 (m-As)(PPh 3 ) 4 ] þ does not display the classical tetrahedral geometry towards the As center [95].…”

Section: Clustering Of Gold Atoms At One Centermentioning

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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“…Für die Phosphoranaloga wurde vorausgesagt, dass die C 4 v ‐Struktur energetisch stabiler ist als die C 3 v ‐Struktur; diese ist wiederum stabil gegenüber der T d ‐Struktur. Schmidbaur und Mitarbeiter133, 134 haben über derartige tetragonale P(AuL) 4 + ‐Strukturen (mit einem fünften apikalen Goldatom) berichtet. Diese Beispiele zeigen, dass die Aurophilie die Tendenz des Zentralatoms, eine tetraedrische sp 3 ‐Koordinationsumgebung aufzubauen, übertreffen kann.…”

Section: Ergebnisse Theoretischer Studienunclassified