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Tri‐ and Tetranuclear Metal‐String Complexes with Metallophilic d 10 –d 10 Interactions
Author(s) -
Olaru Marian,
Kögel Julius F.,
Aoki Risa,
Sakamoto Ryota,
Nishihara Hiroshi,
Lork Enno,
Mebs Stefan,
Vogt Matthias,
Beckmann Jens
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201904106
Subject(s) - tetrahydrothiophene , bimetallic strip , chemistry , crystallography , stereochemistry , ligand (biochemistry) , metal , receptor , organic chemistry , biochemistry
The reaction of 2,6‐F 2 C 6 H 3 SiMe 3 with Ph 2 PLi provided 2,6‐(Ph 2 P) 2 C 6 H 3 SiMe 3 ( 1 ), which can be regarded as precursor for the novel anionic tridentate ligand [2,6‐(Ph 2 P) 2 C 6 H 3 ] − ( PCP ) − . The reaction of 1 with [AuCl(tht)] (tht=tetrahydrothiophene) afforded 2,6‐(Ph 2 PAuCl) 2 C 6 H 3 SiMe 3 ( 2 ). The subsequent reaction of 2 with CsF proceeded with elimination of Me 3 SiF and yielded the neutral tetranuclear complex linear ‐[Au 4 Cl 2 ( PCP ) 2 ] ( 3 ) comprising a string‐like arrangement of four Au atoms. Upon chloride abstraction from 3 with NaBAr F 4 (Ar F =3,5‐(CF 3 ) 2 C 6 H 3 ) in the presence of tht, the formation of the dicationic tetranuclear complex linear ‐[Au 4 ( PCP ) 2 (tht) 2 ](BAr F 4 ) 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 ‐[Au 4 ( PCP ) 2 (tht) 2 ](BAr F 4 ) ( 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 HgCl 2 yielded the neutral trinuclear bimetallic complex [HgAu 2 Cl 3 ( 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 Hg II and the anionic tridentate ligand [2,6‐(Ph 2 PAuCl) 2 C 6 H 3 ] − ( 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.