X-Ray Crystal Structures and Quantum Chemical Calculations of Tetraphenyl-arsonium Tetraazidoaurate(III) and Azido(triphenylphosphine)Gold(I)

Abstract

The single crystal X-ray structure determinations are reported for [Ph 4 As][Au(N 3 ) 4 ] (1) and Ph 3 PAuN 3 (2). Compound 1 is an ionic species with a ªwindmillº shaped anion. It crystallizes in the monoclinic space group C2/c, a = 18.396(2), b = 6.2492(4), c = 23.555(2) A Ê ; b = 107.98(1)°, Z = 4, R1 (all data) = 0.0227, wR2 = 0.0374. The lattice parameters of compound 2, which crystallizes in the orthorhombic space group P2 1 2 1 2 1 , are a = 10.9252(1), b = 11.5642(1), c = 13.0993(1) A Ê ; Z = 4, R1 (all data) = 0.0176, wR = 0.0334.The experimentally obtained X-ray data and vibrational frequencies of both compounds were compared with those calculated at B3LYP/LANL2DZ and B3LYP/SDD level of theory and for 1 also at the MP2/SDD level. Einkristallro È ntgenstrukturanalyse und ab Initio Rechnungen von Tetraphenylarsoniumtetraazidoaurat(III) und Azido(triphenylphosphin)gold(I) Inhaltsu È bersicht. Die Einkristallro È ntgenstrukturanalysen von [Ph 4 As][Au(N 3 ) 4 ](1) und Ph 3 PAuN 3 (2) werden beschrieben. 1 ist eine ionische Verbindung nit einem ¹Windradª-fo È rmigen Anion. Sie kristallisiert in der monoklinen Raumgruppe C2/c, a = 18.396(2), b = 6.2492(4), c = 23.555(2) A Ê ; b = 107.98(1)°, Z = 4, R1 (alle Daten) = 0.0227, wR2 = 0.0374. Die Gitterparameter von Verbindung 2, welche in der orthorhombischen Raumgruppe P2 1 2 1 2 1 kristallisiert, sind a = 10.9252(1), b = 11.5642(1), c = 13.0993(1) A Ê ; Z = 4, R1 (alle Daten) = 0.0176, wR2 = 0.0334. Die experimentell beobachteten Ro È ntgendaten und die Schwingungsfrequenzen beider Verbindungen werden mit denen auf B3LYP/LANL2DZ-und B3LYP/ SDD-Niveau und fu È r 1 auch auf MP2/SDD-Niveau berechneten Daten verglichen.

The Preparation of a Residue‐free, Alumina‐supported Gold Catalyst by Decomposition of an Azido‐Gold(III) Complex and an Evaluation of the Effectiveness of the Catalyst for the Hydrogenation of Propyne

“…The red‐orange salt is an extremely shock‐sensitive material, which exploded spontaneously during several attempts of solvent evaporation, similar as reported for Group 1 cation salts 24–26. However, this ammonium salt can be handled with absolute caution in methanol solutions,5 whereas tetraazidoaurates(III) containing large cations are relatively safe to handle 24–28…”

Azide Chemistry – An Inorganic Perspective, Part I Metal ­Azides: Overview, General Trends and Recent Developments

“…This phenomenon typically caused by the close proximity of heavy and light atoms was also reported, e.g. for SbCl(N 3 ) 2 63, NBu n 4 [Ir(N 3 )pc(acac)] (pc = phthalocyaninate(2‐))64, [IrCp*(N 3 )bipy]PF 6 65, (AsPh 4 ) 2 [Pd 2 (N 3 ) 4 Cl 2 ]58, [N(PPh 3 ) 2 ] 2 [Pd(N 3 ) 4 ]58, [Me 3 PtN 3 ] 4 66, trans ‐[Pt(Me)N 3 (PPr i 3 ) 2 ]62, (AsPh 4 ) 2 [Pt(N 3 ) 4 ]67, (AsPh 4 ) 2 [Pt(N 3 ) 6 ]58,67, (PPh 4 ) 2 [Pt(N 3 ) 6 ], (AsPh 4 ) 2 [Pt(N 3 )Cl 5 ]HCONMe 2 68, and Au(N 3 )(PPh 3 )59b.…”

A Neutral, Carbene-Stabilized Gold(III) Triazide

“…They were the first to identify the orange compound as the sodium salt of the tetraazidoaurate anion [Au­(N 3 ) 4 ] − . One year later, Beck isolated the stable tetraphenylarsonium derivative [Ph 4 As]­[Au­(N 3 ) 4 ], which was spectroscopically (IR and UV) and, later also structurally characterized. − The solid-state structures of the explosive K + , Rb + , Cs + , NH 4 + , and Me 4 N + salts were reported more recently. , The reactivity of the tetraazidoaurate anion has also been investigated. It reacts in a 1,3-dipolar cycloaddition reaction with isonitriles to give the corresponding C-bound gold­(III) tetrazolate derivatives, which was confirmed by an X-ray diffraction study of the product. ,, THF solutions of [Ph 4 As]­[Au­(N 3 ) 4 ] on exposure to light are reduced to the colorless diazidoaurate­(I) salt [Ph 4 As]­[Au­(N 3 ) 2 ]. , Similarly, reduction to gold­(I) occurs when [Ph 4 As]­[Au­(N 3 ) 4 ] is treated with CO, forming the diisocyanatoaurate­(I) salt [Ph 4 As]­[Au­(NCO) 2 ] .…”

“…1.14 Å). The other bond distances and angles are within the expected ranges and are similar to those observed in the tetraazidoaurate salts. − The carbon–gold bond length of 2.011 Å is also typical for a gold­(III)–NHC complex …”