Synthesis and characterization of gold(III) adducts and cyclometallated derivatives with 6-benzyl- and 6-alkyl-2,2′-bipyridines
- 1 January 1996
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 22,p. 4217-4225
- https://doi.org/10.1039/dt9960004217
Abstract
The reaction of a series of 6-substituted-2,2′-bipyridines HL (N2C10H7R, R = CH2Ph, CHMePh, CMe2Ph, CH2Me, CMe3 or CH2CMe3) with HAuCl4 or Na[AuCl4] has been investigated. Under different experimental conditions, salts [H2L][AuCl4], adducts [Au(HL)Cl3] or cyclometallated derivatives [Au(L)Cl][X](X = AuCl4, BF4 or PF6) have been isolated. The cyclometallated species arise from direct activation of a C–H bond either of a phenyl or a methyl substituent. The structures of an adduct [Au{N2C10H7(CHMePh)-6}Cl3] and two metallated species [Au{N2C10H7(CMe2C6H4)-6}Cl][AuCl4] and [Au{N2C10H7(CMe2CH2)-6}Cl][BF4]·0.5H2O have been determined by X-ray diffraction. In the adduct the gold atom is bonded to the nitrogen atom of the unsubstituted pyridine ring: a long-range interaction with the other nitrogen atom is observed, Au ⋯ N 2.758(4)Å. In the two cyclometallated species the bipyridines act as tridentate N,N,C anions, giving a [5,6] and a [5,5]-fused ring system, respectively. In [Au{N2C10H7(CMe2C6H4)-6}Cl]+ the hexaatomic N,C ring adopts a boat-like conformation: the structure reveals a rather short interaction between one hydrogen of the Me group in axial position and the gold atom, Au ⋯ H 2.62 Å. The pentaatomic N,C ring in [Au{N2C10H7(CMe2CH2)-6}Cl]+ is not planar: the co-ordination around the gold atom is essentially square planar. The new cyclometallated complexes [Au(N,N,C)Cl]+ are compared with those derived from similarly substituted pyridines described previously.Keywords
This publication has 28 references indexed in Scilit:
- Cyclometallated derivatives of platinum(II) derived from 6-(tert-butyl)-2,2′-bipyridine (HL). Crystal and molecular structure of [Pt(L)CI]J. Chem. Soc., Dalton Trans., 1995
- Gold(III) Photooxidants. Photophysical, Photochemical Properties, and Crystal Structure of a Luminescent Cyclometalated Gold(III) Complex of 2,9-Diphenyl-1,10-PhenanthrolineInorganic Chemistry, 1994
- Rigid five- and six-membered C,N,N'-bound aryl-, benzyl-, and alkylorganopalladium complexes: sp2 vs. sp3 carbon-hydrogen activation during cyclopalladation and palladium(IV) intermediates in oxidative addition reactions with dihalogens and alkyl halidesOrganometallics, 1993
- Skeletal vibrational spectra of LAuCl3 complexes with heterocyclic nitrogen donorsJournal of Raman Spectroscopy, 1993
- Synthesis and characterization of metalated and cyclometalated platinum(II) and platinum(IV) complexes of .beta.-diestersOrganometallics, 1989
- C–H activation of acetone by 2-phenylazophenylgold(III) complexes; synthesis of the first acetonylgold(III) complexJournal of the Chemical Society, Chemical Communications, 1989
- Chemistry of heterocyclic compounds. 132. Metallocyclic complexes of palladium(II) and platinum(II) containing six- and seven-membered chelate ringsOrganometallics, 1988
- Some attempts to prepare five-co-ordinated gold(III) complexes. Crystal and molecular structures of [Au(C6H4CH2NMe2-2)(phen)(PPh3)][BF4]2·CH2Cl2, [Au(C6H4CH2NMe2-2)(NC9H6O)]BF4, and [Au(C6H4CH2NMe2-2)(H2NC6H4S)]ClO4J. Chem. Soc., Dalton Trans., 1986
- Five-co-ordinated gold(III) complexes. Part 1. Synthesis, structure, and properties of bromodicyano(1,10-phenanthroline)gold(III)–dimethylformamide (1/1)J. Chem. Soc., Dalton Trans., 1986
- Synthesis, structure, and properties of trichloro- and tribromo(2-(2'-pyridyl)quinoline)gold(III)Inorganic Chemistry, 1978