DOI: 10.1002/zaac.19936190913. Some Tris[(triorganophosphine)gold(I)]‐oxonium and ‐Organoimonium Tetrafluoroborates with Bulky Substituents

Some Tris[(triorganophosphine)gold(I)]‐oxonium and ‐Organoimonium Tetrafluoroborates with Bulky Substituents

10.1002/zaac.19936190913

Crossref journal-article

Wiley

Zeitschrift für anorganische und allgemeine Chemie (311)

Abstract

AbstractTris{[tri(2‐methylphenyl)phosphine]gold(I)}‐, tris{[tri(2,4,6‐trimethylphenyl)phosphine]gold(I)}‐ and tris{[tri(cyclohexyl)phosphine]gold(I)}‐oxonium tetra‐fluoroborate (1−3) have been prepared from the corresponding (phosphine)gold(I) chlorides, silver oxide, and sodium tetrafluoroborate in acetone. These oxonium salts are excellent aurating agents for primary amines. Thus in the reaction with 1, t‐butylamine tBuNH2 and aniline PhNH2 are readily converted into the trinuclear imino complexes {[(2‐MeC6H4)3P]Au}3NtBu+BF4− (4) and {[(2‐MeC6H4)3P]Au}3NPh+BF (5) in high yields. With 3, both aniline and 8‐amino‐quinoline also give the trinuclear complexes, i.e. {[(c‐C6H11)3P]Au}3 NPh+BF (6) and {[(c‐C6H11)3P]Au}3N(C9H6N)+BF (7). Auration of aniline with the most sterically hindered reagent 2 yields only the binuclear complex {[2,4,6‐Me3C6H2)3P] · Au}2N(Ph)H+BF (8). The reagents 1−3 and the Products 4–8 have been characterized by analytical and NMR spectroscopic data, and the crystal structures of compounds 4 and 6 have been determined by single crystal x‐ray diffraction. In the cations of 4, a triangle of gold atoms with short Au — Au contacts [3.036(1), 3.107(1), and 3.214(1) Å] forms a steep pyramid with the nitrogen atom, in which the angles AuNAu are all much smaller than the tetrahedral standard of 109.7°: 94.8(4), 98.1(4), and 103.0(4)°. This triangular Au3 unit is staggered relative to the three methyl groups of the tBu substituent at nitrogen. The results for 6 are similar [Au — Au: 3.037(1), 3.071(1), and 3.222(1) Å; AuNAu: 95.3(3), 96.5(3), and 103.6(3)°]. Variable temperature NMR studies of compounds 3 and 8 show hindered rotation of the mesityl groups about the PC bonds of the ligands originating from the steric congestion within each tertiary phosphine.

Bibliography

Kolb, A., Bissinger, P., & Schmidbaur, H. (1993). Some Tris[(triorganophosphine)gold(I)]âoxonium and âOrganoimonium Tetrafluoroborates with Bulky Substituents. Zeitschrift FÃ¼r Anorganische Und Allgemeine Chemie, 619(9), 1580â1588. Portico.

Authors 3

Andreas Kolb (first)
Peter Bissinger (additional)
H. Schmidbaur (additional)

References 30 Referenced 28

10.1179/030801892789816118
10.1007/BF03214710
10.1002/anie.198815441
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10.1002/anie.199013991
10.1002/cber.19921251214
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{'key': 'e_1_2_1_9_2', 'first-page': '783', 'volume': '1991', 'author': 'Grohmann A.', 'journal-title': 'J. Chem. Soc., Dalton Trans.'} / J. Chem. Soc., Dalton Trans. by Grohmann A.
10.1021/ic00343a016
10.1021/ic00047a026
H.Schmidbaur O.Steigelmann Z. Naturforsch. i. pr.
{'key': 'e_1_2_1_13_2', 'first-page': '2277', 'author': 'Jones P. G.', 'year': '1980', 'journal-title': 'Acta Crystallogr.'} / Acta Crystallogr. by Jones P. G. (1980)
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{'key': 'e_1_2_1_17_2', 'first-page': '11', 'volume': '23', 'author': 'Schmidbaur H.', 'year': '1990', 'journal-title': 'Inorg. Chem.'} / Inorg. Chem. by Schmidbaur H. (1990)
10.1038/352141a0
10.1016/S0022-328X(00)92589-0
P. R.Sharp private communication.
10.1021/ja00030a084
the structure of a second form of [(Ph3PAu)3O]+BFwas determined independently byH.Schmidbaur E.Zeller A.Schier(unpublished data1992).
10.1021/cr60307a002
{'key': 'e_1_2_1_23_2', 'first-page': '523', 'volume': '2', 'author': 'Perevalova E. G.', 'year': '1989', 'journal-title': 'Organomet. Chem. USSR'} / Organomet. Chem. USSR by Perevalova E. G. (1989)
10.1002/9780470132548.ch39
{'key': 'e_1_2_1_25_2', 'volume-title': 'SHELXS 86 in Crystallographic Computing 3', 'author': 'Sheldrick G. M.', 'year': '1985'} / SHELXS 86 in Crystallographic Computing 3 by Sheldrick G. M. (1985)
{'key': 'e_1_2_1_26_2', 'volume-title': 'SHELX 76, Program for Crystal Structure Determination', 'author': 'Sheldrick G. M.', 'year': '1976'} / SHELX 76, Program for Crystal Structure Determination by Sheldrick G. M. (1976)

Dates

Type	When
Created	20 years, 8 months ago (Jan. 2, 2005, 5:40 a.m.)
Deposited	1 year, 11 months ago (Sept. 27, 2023, 1 p.m.)
Indexed	1 year, 3 months ago (June 3, 2024, 7:16 p.m.)
Issued	32 years ago (Sept. 1, 1993)
Published	32 years ago (Sept. 1, 1993)
Published Online	20 years, 9 months ago (Nov. 9, 2004)
Published Print	32 years ago (Sept. 1, 1993)

Funders 0

None

BibTeX

@article{Kolb_1993, title={Some Tris[(triorganophosphine)gold(I)]‐oxonium and ‐Organoimonium Tetrafluoroborates with Bulky Substituents}, volume={619}, ISSN={1521-3749}, url={http://dx.doi.org/10.1002/zaac.19936190913}, DOI={10.1002/zaac.19936190913}, number={9}, journal={Zeitschrift für anorganische und allgemeine Chemie}, publisher={Wiley}, author={Kolb, Andreas and Bissinger, Peter and Schmidbaur, H.}, year={1993}, month=sep, pages={1580–1588} }

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  "abstract": "<jats:title>Abstract</jats:title><jats:p>Tris{[tri(2\u2010methylphenyl)phosphine]gold(I)}\u2010, tris{[tri(2,4,6\u2010trimethylphenyl)phosphine]gold(I)}\u2010 and tris{[tri(cyclohexyl)phosphine]gold(I)}\u2010oxonium tetra\u2010fluoroborate (<jats:bold>1\u22123</jats:bold>) have been prepared from the corresponding (phosphine)gold(I) chlorides, silver oxide, and sodium tetrafluoroborate in acetone. These oxonium salts are excellent aurating agents for primary amines. Thus in the reaction with <jats:bold>1, t</jats:bold>\u2010butylamine <jats:sup>t</jats:sup>BuNH<jats:sub>2</jats:sub> and aniline PhNH<jats:sub>2</jats:sub> are readily converted into the <jats:bold>tri</jats:bold>nuclear imino complexes {[(2\u2010MeC<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>)<jats:sub>3</jats:sub>P]Au}<jats:sub>3</jats:sub>N<jats:sup>t</jats:sup>Bu<jats:sup>+</jats:sup>BF<jats:sub>4</jats:sub><jats:sup>\u2212</jats:sup> (<jats:bold>4</jats:bold>) and {[(2\u2010MeC<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>)<jats:sub>3</jats:sub>P]Au}<jats:sub>3</jats:sub>NPh<jats:sup>+</jats:sup>BF<jats:inline-graphic xmlns:xlink=\"http://www.w3.org/1999/xlink\" xlink:href=\"graphic/tex2gif-stack-1.gif\" xlink:title=\"urn:x-wiley:00442313:media:ZAAC19936190913:tex2gif-stack-1\" /> (<jats:bold>5</jats:bold>) in high yields. With <jats:bold>3</jats:bold>, both aniline and 8\u2010amino\u2010quinoline also give the <jats:bold>tri</jats:bold>nuclear complexes, i.e. {[(c\u2010C<jats:sub>6</jats:sub>H<jats:sub>11</jats:sub>)<jats:sub>3</jats:sub>P]Au}<jats:sub>3</jats:sub> NPh<jats:sup>+</jats:sup>BF<jats:inline-graphic xmlns:xlink=\"http://www.w3.org/1999/xlink\" xlink:href=\"graphic/tex2gif-stack-2.gif\" xlink:title=\"urn:x-wiley:00442313:media:ZAAC19936190913:tex2gif-stack-2\" /> (<jats:bold>6</jats:bold>) and {[(c\u2010C<jats:sub>6</jats:sub>H<jats:sub>11</jats:sub>)<jats:sub>3</jats:sub>P]Au}<jats:sub>3</jats:sub>N(C<jats:sub>9</jats:sub>H<jats:sub>6</jats:sub>N)<jats:sup>+</jats:sup>BF<jats:inline-graphic xmlns:xlink=\"http://www.w3.org/1999/xlink\" xlink:href=\"graphic/tex2gif-stack-3.gif\" xlink:title=\"urn:x-wiley:00442313:media:ZAAC19936190913:tex2gif-stack-3\" /> (<jats:bold>7</jats:bold>). Auration of aniline with the most sterically hindered reagent <jats:bold>2</jats:bold> yields only the <jats:bold>bi</jats:bold>nuclear complex {[2,4,6\u2010Me<jats:sub>3</jats:sub>C<jats:sub>6</jats:sub>H<jats:sub>2</jats:sub>)<jats:sub>3</jats:sub>P] \u00b7 Au}<jats:sub>2</jats:sub>N(Ph)H<jats:sup>+</jats:sup>BF<jats:inline-graphic xmlns:xlink=\"http://www.w3.org/1999/xlink\" xlink:href=\"graphic/tex2gif-stack-4.gif\" xlink:title=\"urn:x-wiley:00442313:media:ZAAC19936190913:tex2gif-stack-4\" /> (<jats:bold>8</jats:bold>). The reagents <jats:bold>1\u22123</jats:bold> and the Products <jats:bold>4</jats:bold>\u2013<jats:bold>8</jats:bold> have been characterized by analytical and NMR spectroscopic data, and the crystal structures of compounds <jats:bold>4</jats:bold> and <jats:bold>6</jats:bold> have been determined by single crystal x\u2010ray diffraction. In the cations of <jats:bold>4</jats:bold>, a triangle of gold atoms with short Au \u2014 Au contacts [3.036(1), 3.107(1), and 3.214(1) \u00c5] forms a steep pyramid with the nitrogen atom, in which the angles Au\uf8ffN\uf8ffAu are all much smaller than the tetrahedral standard of 109.7\u00b0: 94.8(4), 98.1(4), and 103.0(4)\u00b0. This triangular Au<jats:sub>3</jats:sub> unit is staggered relative to the three methyl groups of the <jats:sup>t</jats:sup>Bu substituent at nitrogen. The results for <jats:bold>6</jats:bold> are similar [Au \u2014 Au: 3.037(1), 3.071(1), and 3.222(1) \u00c5; Au\uf8ffN\uf8ffAu: 95.3(3), 96.5(3), and 103.6(3)\u00b0]. Variable temperature NMR studies of compounds <jats:bold>3</jats:bold> and <jats:bold>8</jats:bold> show hindered rotation of the mesityl groups about the P\uf8ffC bonds of the ligands originating from the steric congestion within each tertiary phosphine.</jats:p>",
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