[{(H3C)3NB(H)2NC}2Au][AuI2]: a linear chain polymer of gold(I) iodide with an unusual isocyanoborane ligand showing aurophilic behaviour

Kaska, William C.; Mayer, Hermann A.; Elsegood, Mark R. J.; Hursthouse, Michael B.; Redshaw, Carl; Humphrey, Simon M.

doi:10.1107/s1600536804008098

Cited by 6 publications

(5 citation statements)

References 5 publications

(2 reference statements)

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“…All the M−I bond lengths in the coinage diiodide complexes are within the range of the M−I covalent single-bond lengths (2.45, 2.61, and 2.57 Å for Cu, Ag, Au, respectively) estimated by the self-consistent covalent radii derived by Pyykkö . The optimized Au−I distance of 2.58 Å at CCSD((T) level is consistent with the experimental distances in [AuI 2 ] − units found in crystals (2.529, 2.5604, and 2.7713 Å). − The PBE-optimized Cs−I distance is 0.06 Å shorter than the sum of the covalent radii.…”

Section: Discussionsupporting

confidence: 83%

Photoelectron Imaging and Spectroscopy of MI₂⁻ (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding

Wang

Xing

et al. 2010

J. Phys. Chem. A

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We report a combined experimental and theoretical investigation of MI(2)(-) (M = Cs, Cu, Ag, Au) to explore the chemical bonding in the group IA and IB diiodide complexes. Both photoelectron imaging and low-temperature photoelectron spectroscopy are applied to MI(2)(-) (M = Cs, Cu, Au), yielding vibrationally resolved spectra for CuI(2)(-) and AuI(2)(-) and accurate electron affinities, 4.52 ± 0.02, 4.256 ± 0.010, and 4.226 ± 0.010 eV for CsI(2), CuI(2), and AuI(2), respectively. Spin-orbit coupling is found to be important in all the diiodide complexes and ab initio calculations including spin-orbit effects allow quantitative assignments of the observed photoelectron spectra. A variety of chemical bonding analyses (charge population, bond order, and electron localization functions) have been carried out, revealing a gradual transition from the expected ionic behavior in CsI(2)(-) to relatively strong covalent bonding in AuI(2)(-). Both relativistic effects and electron correlation are shown to enhance the covalency in the gold diiodide complex.

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Section: Discussionsupporting

confidence: 83%

Photoelectron Imaging and Spectroscopy of MI₂⁻ (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding

Wang

Xing

et al. 2010

J. Phys. Chem. A

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“…The structure of 3 was determined by X-ray diffraction and has been reported recently. 24 Compound 3 is an unexpected product of formula [(RNC) 2 Au][AuI 2 ], which consists of a perfectly linear one-dimensional chain of pseudoorthogonally aligned alternating cation, anion gold(I) units (Fig. 6).…”

Section: Bis(trimethylamine-isocyanoborane)gold(i) Diiodogold(i)mentioning

confidence: 99%

Variable solid state aggregations in a series of (isocyanide)gold(i) halides with the novel trimethylamine-isocyanoborane adduct

et al. 2005

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This paper provides evidence that the degree of aurophilic character and resulting solid state arrangement observed in (isocyanide)gold(I) halides is in part dependent on the nature of halide substituent. In particular, we report here the synthesis of a series of novel (isocyanide)gold(I) halides involving trimethylamine-isocyanoborane, an unusual 'zwitterionic' isocyanide that is comparable to the more familiar methyl isocyanide, but potentially more strongly Lewis basic. The reaction of chloro(dimethyl sulfide)gold(I) and the isocyanoborane species, (RNC)(R =(H3C)3NB(H)2), gives the novel crystalline adduct [(RNC)AuCl] (1). Treatment of 1 in an organic phase with aqueous KBr effected substitution of the chloride to give the bromide analogue [(RNC)AuBr] (2). The structures of 1 and 2 were determined by X-ray crystallography to be isostructural, consisting of a zigzag topology of chains of monomers, where adjacent gold(I) centres interact aurophilically. However, similar reaction of 1 with KI solution affords the unusual and unexpected compound, [(RNC)2Au][AuI2] (3). This iodide 3, is a linear chain polymer of alternating anion, cation units that is formed via ligand redistribution. The complexes 1-3 all fluoresce in the presence of UV light; the fluorescence of 3 being most prevalent at room temperature. The free trimethylamine-isocyanoborane ligand, the dimeric structures of compounds 1,2 and the thermodynamic stabilities of the dimers in the gas phase were studied by density functional and ab initio calculations at various levels of theory. The theoretical results are compared to the corresponding experimental data.

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“…Examples for a ligand redistribution forming the ionic species [(R 3 P) 2 studied in this survey exist in the neutral form in the solid state [11]. In the case of ligands L with carbon, nitrogen or sulphur donor atoms, the ionic form [L 2 Au][AuX 2 ] can be found more frequently [12][13][14][15] and some of the complexes showing this binding pattern in their crystals are [(s-py) 2 Au][AuX 2 ] (s-py = substituted pyridine, X = Cl, Br, I) [12], [{(R 2 N) 2 C=NH} 2 Au][AuX 2 ] (R = Me, Ph, X = Cl, Br) [13], [(tht) 2 Au][AuI 2 ] [14], and [( t BuNC) 2 Au][AuI 2 ](I 2 ) [16]. All of these complexes are additionally stabilized by aggregation via aurophilic contacts.…”

mentioning

confidence: 98%

Unprecedented coordination chemistry of a chloro(phosphine)gold(I) complex: [(Ad2BnP)2Au][AuCl2]

Monkowius¹,

Zabel²,

Yersin³

2008

Inorganic Chemistry Communications

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[{(H₃C)₃NB(H)₂NC}₂Au][AuI₂]: a linear chain polymer of gold(I) iodide with an unusual isocyanoborane ligand showing aurophilic behaviour

Abstract: metal-organic papers m564 William C. Kaska et al. [Au(C 4 H 11 BN 2) 2 ][AuI 2 ] Acta Cryst. (2004). E60, m563±m565 Acta Cryst. (2004). E60, m563±m565 William C. Kaska et al. [Au(C 4 H 11 BN 2) 2 ][AuI 2 ] m565 metal-organic papers

Cited by 6 publications

References 5 publications

Photoelectron Imaging and Spectroscopy of MI₂⁻ (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding

Photoelectron Imaging and Spectroscopy of MI₂⁻ (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding

Variable solid state aggregations in a series of (isocyanide)gold(i) halides with the novel trimethylamine-isocyanoborane adduct

Unprecedented coordination chemistry of a chloro(phosphine)gold(I) complex: [(Ad2BnP)2Au][AuCl2]

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[{(H3C)3NB(H)2NC}2Au][AuI2]: a linear chain polymer of gold(I) iodide with an unusual isocyanoborane ligand showing aurophilic behaviour

Abstract: metal-organic papers m564 William C. Kaska et al. [Au(C 4 H 11 BN 2) 2 ][AuI 2 ] Acta Cryst. (2004). E60, m563±m565 Acta Cryst. (2004). E60, m563±m565 William C. Kaska et al. [Au(C 4 H 11 BN 2) 2 ][AuI 2 ] m565 metal-organic papers

Cited by 6 publications

References 5 publications

Photoelectron Imaging and Spectroscopy of MI2− (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding

Photoelectron Imaging and Spectroscopy of MI2− (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding

Variable solid state aggregations in a series of (isocyanide)gold(i) halides with the novel trimethylamine-isocyanoborane adduct

Unprecedented coordination chemistry of a chloro(phosphine)gold(I) complex: [(Ad2BnP)2Au][AuCl2]

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[{(H₃C)₃NB(H)₂NC}₂Au][AuI₂]: a linear chain polymer of gold(I) iodide with an unusual isocyanoborane ligand showing aurophilic behaviour

Photoelectron Imaging and Spectroscopy of MI₂⁻ (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding

Photoelectron Imaging and Spectroscopy of MI₂⁻ (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding