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Heterometallic Complexes with Gold(I) Metalloligands: Self‐Assembly of Helical Dimers Stabilized by Weak Intermolecular Interactions and Solvophobic Effects
Author(s) -
Cámara Verónica,
Barquero Natalia,
Bautista Delia,
GilRubio Juan,
Vicente José
Publication year - 2015
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.201405487
Subject(s) - solvophobic , chemistry , intermolecular force , solvent , crystallography , stereochemistry , rhodium , single crystal , catalysis , molecule , organic chemistry
New gold(I) alkynyl metalloligands bpylCCAuL, bpyl′CCAuPPh 3 , and PPN[Au(CCbpyl′) 2 ] (bpyl or bpyl′=2,2′‐bipyridin‐5‐yl or −4‐yl, respectively; L=PMe x Ph 3− x ( x =1–3), P(C 6 H 3 Me 2 ‐3,5) 3 , PCy 3 , XyNC) have been synthesized. Ligands bpylCCH and metalloligands bpylCCAuL (L=PPh 3 , PMePh 2 , PCy 3 , CNXy) react with MX 2 (M=Fe, Zn, X=ClO 4 ; M=Co, X=BF 4 ) to give complexes [M(bpylCCZ) 3 ]X 2 (Z=H or AuL). In most cases, these complexes are mixtures of fac and mer isomers in a statistical distribution, in both CH 2 Cl 2 and MeCN. However, for L=PPh 3 , the fac isomer is dominant in MeCN. NMR and ESI‐MS studies, together with the crystal structure of [Co(bpylCCAuPPh 3 ) 3 ](BF 4 ) 2 , suggest that this solvent dependence is originated by the formation of helical dimers between two fac complexes in MeCN. These dimers are stabilized by solvophobic effects and multiple intermolecular interactions. Complex [Fe(Ph 3 PAuCCbpdiylCCAuPPh 3 ) 3 ](ClO 4 ) 2 (bpdiyl=2,2′‐bipyridin‐5,5′‐diyl) was obtained by reaction of three diauro diethynylbipyridines and Fe(ClO 4 ) 2 .