396. The action of nitrosyl chloride on some metals and their compounds

Partington, J. R.; Whynes, A. L.

doi:10.1039/jr9480001952

Cited by 15 publications

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“…[GaCl 4 ] − is known to stabilize reactive cations like [Au(P 4 ) 2 ] + , [P 5 Ph 2 ] + , and [P 2 Ph 5 ] + . However, little characterization has been carried out on [NO] + [GaCl 4 ] − ( 1 b )—prepared from an excess of gaseous NOCl and elemental gallium or GaCl 3 —apart from Raman spectroscopy . We were interested in whether reaction (1) would deliver 1 b in a more straightforward manner.…”

Section: Resultsmentioning

confidence: 99%

“…[GaCl 4 ] À is known to stabilize reactive cations like [Au(P 4 ) 2 ] + , [39] [P 5 Ph 2 ] + , [40] and [P 2 Ph 5 ] + . [41] However,l ittle characterization has been carriedo ut on [NO] + [GaCl 4 ] À (1b)-prepared from an excesso fg aseous NOCl and elemental gallium [42] or GaCl 3 [43] -apart from Ramans pectroscopy. [44] We were interested in whether reaction (1)w ould deliver 1b in am ore straightforward manner.T he WCA [B(CF 3 ) 4 ] À is prepared by stepwise fluorination of M + [B(CN) 4 ] À (M = Li, K, Cs, Ag) with ClF 3 in anhydrous HF, [45] and the entire series [46,47] The originals ynthesis of [NO] + [B(CF 3 ) 4 ] À included metathesis to the guanidinium salt, oxidationw ith excess NO 2 ,a nd concomitant reduction to…”

Section: Synthesis Of Nitrosyl Salts Of Weakly Coordinating Anionsmentioning

confidence: 99%

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Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?

Engesser

Friedmann

Martens

et al. 2016

Chemistry A European J

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A series of gold acetonitrile complexes [Au(NCMe) ] [WCA] with weakly coordinating counterions (WCAs) was synthesized by the reaction of elemental gold and nitrosyl salts [NO] [WCA] in acetonitrile ([WCA] =[GaCl ] , [B(CF ) ] , [Al(OR ) ] ; R =C(CF ) ). In the crystal structures, the [Au(NCMe) ] units appeared as monomers, dimers, or chains. A clear correlation between the aurophilicity and the coordinating ability of counterions was observed, with more strongly coordinating WCAs leading to stronger aurophilic contacts (distances, C-N stretching frequencies of [Au(NCMe) ] units). An attempt to prepare [Au(L) ] units, even with less weakly basic solvents like CH Cl , led to decomposition of the [Al(OR ) ] anion and formation of [NO(CH Cl ) ] [F(Al(OR ) ) ] . All nitrosyl reagents [NO] [WCA] were generated according to an optimized procedure and were thoroughly characterized by Raman and NMR spectroscopy. Moreover, the to date unknown species [NO] [B(CF ) CN] was prepared. Its reaction with gold unexpectedly produced [Au(NCMe) ] [Au(NCB(CF ) ) ] , in which the cyanoborate counterion acts as an anionic ligand itself. Interestingly, the auroborate anion [Au(NCB(CF ) ) ] behaves as a weakly coordinating counterion, which becomes evident from the crystallographic data and the vibrational spectral characteristics of the [Au(NCMe) ] cation in this complex. Ligand exchange in the only room temperature stable salt of this series, [Au(NCMe) ] [Al(OR ) ] , is facile and, for example, [Au(PPh )(NCMe)] [Al(OR ) ] can be selectively generated. This reactivity opens the possibility to generate various [AuL L ] [Al(OR ) ] salts through consecutive ligand-exchange reactions that offer access to a huge variety of Au complexes for gold catalysis.

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Section: Resultsmentioning

confidence: 99%

Section: Synthesis Of Nitrosyl Salts Of Weakly Coordinating Anionsmentioning

confidence: 99%

Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?

Engesser

Friedmann

Martens

et al. 2016

Chemistry A European J

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“…Metallic copper and nitrosyl chloride at 100°C. form CuCl-NOCl (35,125,126,198,376,458). This product is a deliquescent paramagnetic (19) solid.…”

Section: B Metalsmentioning

confidence: 99%

“…Zinc is readily attacked by nitrosyl chloride at room temperature and ZnCl2'NOCl is formed (3,19,59,126,376,458). The nitrosyl chloride in this compound is very lightly held (19).…”

Section: B Metalsmentioning

confidence: 99%

“…Mercury reacts readily with nitrosyl chloride at room temperature liberating nitric oxide (35,74,96,125,126,173,174,198,377,454). HgCl2-NOCl has been made from mercuric chloride (19,170,376) and from mercurous chloride (170, 376) by reaction with nitrosyl chloride at about -20°C. Presumably such a compound could be made from mercury at low temperatures.…”

Section: B Metalsmentioning

confidence: 99%

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Nitrosyl Chloride.

Beckham¹,

Fessler²,

Kise³

1951

Chem. Rev.

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The Raman spectra of the compounds NaCl. ALCL₃ and NOCl. ALCL₃

Gerding

Houtgraaf

1953

Recl. Trav. Chim. Pays‐Bas

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The Raman frequency shifts and the depolarization ratio of the Raman lines have been determined for the compounds NaCl . AICl, and t O C l . AlCl, (in the last case with qualitative polarization measurements only). The preparation of pure NOCl . AlCI, is described in extenso. The properties of the compound finally obtained are different from those given in the literature. NaCl . AlCl, has to be considered as Na+AlCl,-and NOCl . AlCI, as NO+AICI,--. There is a perceptible interaction between nitrosyl and the chlorines of AlC14-in the last compound. The properties of NOCl . AlCl, are intermediate between those for a pure heteropolar compound (NO+AICI,-) and a pure molecular compound NOCl . AICI,, being more alike those of the heteropolar form.Force constants have been calculated for AIC1,--, making use of the Lechner formulae and of those for a Urey-Bradley field and also of those for the orbital valence force field of Heath and Linnett.

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396. The action of nitrosyl chloride on some metals and their compounds

Cited by 15 publications

References 0 publications

Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?

Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?

Nitrosyl Chloride.

The Raman spectra of the compounds NaCl. ALCL₃ and NOCl. ALCL₃

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396. The action of nitrosyl chloride on some metals and their compounds

Cited by 15 publications

References 0 publications

Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?

Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?

Nitrosyl Chloride.

The Raman spectra of the compounds NaCl. ALCL3 and NOCl. ALCL3

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The Raman spectra of the compounds NaCl. ALCL₃ and NOCl. ALCL₃