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Crown Compounds for Anions: Sandwich and Half‐Sandwich Complexes of Cyclic Trimeric Perfluoro‐ o ‐phenylenemercury with Polyhedral closo ‐[B 10 H 10 ] 2− and closo ‐[B 12 H 12 ] 2− Anions
Author(s) -
Shubina Elena S.,
Tikhonova Irina A.,
Bakhmutova Ekaterina V.,
Dolgushin Fedor M.,
Antipin Mikhail Yu.,
Bakhmutov Vladimir I.,
Sivaev Igor B.,
Teplitskaya Lylia N.,
Chizhevsky Igor T.,
Pisareva Irina V.,
Bregadze Vladimir I.,
Epstein Lina M.,
Shur Vladimir B.
Publication year - 2001
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 - 10.1002/1521-3765(20010903)7:17<3783::aid-chem3783>3.0.co;2-1
Subject(s) - chemistry , crystallography , molecule , infrared spectroscopy , ion , x ray crystallography , nuclear magnetic resonance spectroscopy , stereochemistry , diffraction , physics , organic chemistry , optics
It has been shown by IR and NMR spectroscopy that cyclic trimeric perfluoro‐ o ‐phenylenemercury ( o‐ C 6 F 4 Hg) 3 ( 1 ) is capable of binding closo ‐[B 10 H 10 ] 2− and closo ‐[B 12 H 12 ] 2− anions to form complexes [{( o‐ C 6 F 4 Hg) 3 }(B 10 H 10 )] 2− ( 2 ), [{( o‐ C 6 F 4 Hg) 3 } 2 (B 10 H 10 )] 2− ( 3 ), [{( o‐ C 6 F 4 Hg) 3 }(B 12 H 12 )] 2− ( 4 ), and [{( o‐ C 6 F 4 Hg) 3 } 2 (B 12 H 12 )] 2− ( 5 ). According to IR data, the bonding of the [B 10 H 10 ] 2− and [B 12 H 12 ] 2− ions to the macrocycle in these complexes is accomplished through the formation of B‐H‐Hg bridges. Complexes 2, 3 , and 5 have been isolated in analytically pure form and have been characterized by spectroscopic means. X‐ray diffraction studies of 3 and 5 have revealed that these compounds have unusual sandwich structures, in which the polyhedral dianion is located between the planes of two molecules of 1 and is bonded to each of them through two types of B‐H‐Hg bridges. One type is the simultaneous coordination of a B−H group to all three Hg atoms of the macrocycle. The other type is the coordination of a B−H group to a single Hg atom of the cycle. According to X‐ray diffraction data, complex 2 has an analogous but half‐sandwich structure. The obtained complexes 2 – 5 are quite stable; their stability constants in THF/acetone (1:1) at 20 °C have been determined as 1.0×10 2 L mol −1 , 2.6×10 3 L 2 mol −2 , 0.7×10 2 L mol −1 , and 0.98×10 3 L 2 mol −2 , respectively.