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Citation
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HERO ID
6575008
Reference Type
Journal Article
Title
Tri- and Tetranuclear Metal-String Complexes with Metallophilic d10 -d10 Interactions
Author(s)
Olaru, M; Kögel, JF; Aoki, R; Sakamoto, R; Nishihara, H; Lork, E; Mebs, S; Vogt, M; Beckmann, J; ,
Year
2020
Is Peer Reviewed?
Yes
Journal
Chemistry: A European Journal
ISSN:
0947-6539
EISSN:
1521-3765
Publisher
WILEY-V C H VERLAG GMBH
Location
WEINHEIM
Volume
26
Issue
1
Page Numbers
275-284
Language
English
PMID
31584732
DOI
10.1002/chem.201904106
Web of Science Id
WOS:000498593900001
URL
http://
://WOS:000498593900001
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Abstract
The reaction of 2,6-F2 C6 H3 SiMe3 with Ph2 PLi provided 2,6-(Ph2 P)2 C6 H3 SiMe3 (1), which can be regarded as precursor for the novel anionic tridentate ligand [2,6-(Ph2 P)2 C6 H3 ]- (PCP)- . The reaction of 1 with [AuCl(tht)] (tht=tetrahydrothiophene) afforded 2,6-(Ph2 PAuCl)2 C6 H3 SiMe3 (2). The subsequent reaction of 2 with CsF proceeded with elimination of Me3 SiF and yielded the neutral tetranuclear complex linear-[Au4 Cl2 (PCP)2 ] (3) comprising a string-like arrangement of four Au atoms. Upon chloride abstraction from 3 with NaBArF4 (ArF =3,5-(CF3 )2 C6 H3 ) in the presence of tht, the formation of the dicationic tetranuclear complex linear-[Au4 (PCP)2 (tht)2 ](BArF4 )2 (4) was observed, in which the string-like structural motif is retained. Irradiation of 4 with UV light triggered a facile rearrangement in solution giving rise to the dicationic tetranuclear complex cyclo-[Au4 (PCP)2 (tht)2 ](BArF4 ) (5), which comprises a rhomboidal motif of four Au atoms. In 3-5, the Au atoms are associated by a number of significant aurophilic interactions. The atom-economic and selective reaction of 3 with HgCl2 yielded the neutral trinuclear bimetallic complex [HgAu2 Cl3 (PCP)] (6) comprising significant metallophilic interactions between the Au and Hg atoms. Therefore, 6 may be also regarded as a metallopincer complex [ClHg(AuCAu)] between HgII and the anionic tridentate ligand [2,6-(Ph2 PAuCl)2 C6 H3 ]- (AuCAu)- containing a central carbanionic binding site and two "gold-arms" contributing pincer-type chelation trough metallophilic interactions. Compounds 1-6 were characterized experimentally by multinuclear NMR spectroscopy and X-ray crystallography and computationally using a set of real-space bond indicators (RSBIs) derived from electron density (ED) methods including Atoms In Molecules (AIM), the Electron Localizability Indicator (ELI-D) as well as the Non-Covalent Interaction (NCI) Index.
Keywords
gold; ligand design; mercury; metallophilic interactions; metallopincer; closed-shell interactions; polynuclear complexes; crystal-structures; gold(i) complexes; nhc ligands; 2,6-bis(diphenylphosphino)pyridine; trinuclear; example; Chemistry
Tags
IRIS
•
Inorganic Mercury Salts (2)
Mercuric Chloride
Litsearch 2019-2020
PubMed
WoS
Mercurous Chloride
Litsearch 2019-2020
PubMed
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