Facile oxidation of NHC-Au(I) to NHC-Au(III) complexes by CsBr3

被引：31

作者：

Kriechbaum, Margit ^{[1
]}

Otte, Daniela ^{[1
]}

List, Manuela ^{[2
]}

Monkowius, Uwe ^{[1
]}

机构：

[1] Johannes Kepler Univ Linz, Inst Inorgan Chem, A-4040 Linz, Austria

[2] Johannes Kepler Univ Linz, Inst Chem Technol Organ Mat, A-4040 Linz, Austria

来源：

DALTON TRANSACTIONS | 2014年 / 43卷 / 23期

关键词：

N-HETEROCYCLIC CARBENE; GOLD(III) COMPLEXES; COORDINATION CHEMISTRY; ELECTRONIC-STRUCTURES; EXCITED-STATES; LUMINESCENT; BEARING; AU; SILVER(I); REACTIVITY;

D O I：

10.1039/c4dt00695j

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

CsBr3 was investigated as a new and convenient oxidant for NHC-Au(I) complexes (NHC = imidazo[1,5-a]pyridin- 3-ylidene) for the preparation of the respective Au(III) complexes. The Au(I) complexes were synthesized by the silver salt method using [(NHC)(2)Ag] PF6 and (tht) AuBr. Unexpectedly, the reactions yielded both neutral (NHC) AuBr and ionic [(NHC)(2)Au] PF6, depending on the N-substituent of the NHC ligand. Oxidation with CsBr3 gave the complexes (NHC) AuBr3 and [(NHC)(2)AuBr2] PF6 in high yields and purity, which proves the suitability of this reagent. The complexes were further characterised by X-ray diffraction and electronic absorption and emission spectroscopy. The Au(I) complexes exhibit a dual emission attributable to intraligand fluorescence and phosphorescence at both room temperature and 77 K. Upon irradiation with polychromatic light (lambda > 305 nm), the Au(III) complexes are cleanly photo-reduced to the Au(I) congener.

引用

页码：8781 / 8791

页数：11

共 50 条

[1] Luminescent Metallogels of Bis-Cyclometalated Alkynylgold(III) Complexes [J].

Au, Vonika Ka-Man ;

Zhu, Nianyong ;

Yam, Vivian Wing-Wah .

INORGANIC CHEMISTRY, 2013, 52 (02) :558-567

[2]

BRAUER G, 1978, HDB PRAPARATIVEN ANO, V2, P998

[3] Luminescent cyclometalated gold(III) complexes [J].

Bronner, Catherine ;

Wenger, Oliver S. .

DALTON TRANSACTIONS, 2011, 40 (46) :12409-12420

[4] Imidazo[1,5-a]pyridine-3-ylidenes -: pyridine derived N-heterocyclic carbene ligands [J].

Burstein, C ;

Lehmann, CW ;

Glorius, F .

TETRAHEDRON, 2005, 61 (26) :6207-6217

[5] Synthesis, characterization and reactivity of N-heterocyclic carbene gold(III) complexes [J].

de Fremont, Pierre ;

Singh, Rohit ;

Stevens, Edwin D. ;

Petersen, Jeffrey L. ;

Nolan, Steven P. .

ORGANOMETALLICS, 2007, 26 (06) :1376-1385

[6] Gold-Catalyzed Ethynylation of Arenes [J].

de Haro, Teresa ;

Nevado, Cristina .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (05) :1512-+

[7] 1H NMR direct observation of enantiomeric exchange in palladium(II) and platinum(II) complexes containing N,N′ bidentate aryl-pyridin-2-ylmethyl-amine ligands [J].

Diez, Virginia ;

Cuevas, Jose V. ;

Garcia-Herbosa, Gabriel ;

Aullon, Gabriel ;

Charmant, Jonathan P. H. ;

Carbayo, Arancha ;

Munoz, Asuncion .

INORGANIC CHEMISTRY, 2007, 46 (02) :568-577

[8] Shaping and enforcing coordination spheres:: The implications of C3 and C1 chirality in the coordination chemistry of 1,1,1-tris(oxazolinyl)ethane ("trisox") [J].

Gade, Lutz H. ;

Marconi, Guido ;

Dro, Clemence ;

Ward, Benjamin D. ;

Poyatos, Macarena ;

Bellemin-Laponnaz, Stephane ;

Wadepohl, Hubert ;

Sorace, Lorenzo ;

Poneti, Giordano .

CHEMISTRY-A EUROPEAN JOURNAL, 2007, 13 (11) :3058-3075

[9] Electronic and Steric Parameters of 76 N-Heterocyclic Carbenes in Ni(CO)3(NHC) [J].

Gusev, Dmitry G. .

ORGANOMETALLICS, 2009, 28 (22) :6458-6461

[10]

Hashmi A. S. K., 2012, MODERN GOLD CATALYZE

← 1 2 3 4 5 →