Anion-Controlled Switching of an X Ligand into a Z Ligand: Coordination Non-innocence of a Stiboranyl Ligand

The tetravalent platinum stiboranyl complex [(o‐(Ph2P)C6H4)2(o‐C6Cl4O2)Sb]PtCl2Ph (2) has been synthesized by reaction of [(o‐(Ph2P)C6H4)2SbClPh]PtCl (1) with o‐chloranil. In the presence of fluoride anions, the stiboranyl moiety of 2 displays non‐innocent behavior and is readily converted into a fl...

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Published inAngewandte Chemie (International ed.) Vol. 53; no. 10; pp. 2633 - 2637
Main Authors Ke, Iou-Sheng, Jones, James S., Gabbaï, François P.
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 03.03.2014
WILEY‐VCH Verlag
Wiley
Subjects
antimony
Chemistry
Chemistry, Multidisciplinary
fluoride
ligand design
Physical Sciences
platinum
Science & Technology
structure elucidation
OXIDATION
PHOSPHORUS
antimony
CRYSTAL-STRUCTURE
STIBINE
fluoride
PLATINUM(IV) COMPLEXES
CLEAVAGE
platinum
ligand design
CHEMISTRY
structure elucidation
PT-195 NMR
PALLADIUM(II)
CHLORIDE
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Summary:The tetravalent platinum stiboranyl complex [(o‐(Ph2P)C6H4)2(o‐C6Cl4O2)Sb]PtCl2Ph (2) has been synthesized by reaction of [(o‐(Ph2P)C6H4)2SbClPh]PtCl (1) with o‐chloranil. In the presence of fluoride anions, the stiboranyl moiety of 2 displays non‐innocent behavior and is readily converted into a fluorostiborane unit. This transformation, which is accompanied by elimination of a chloride ligand from the Pt center, results in the formation of [(o‐(Ph2P)C6H4)2(o‐C6Cl4O2)SbF]PtClPh (3). Structural, spectroscopic, and computational studies show that the conversion of 2 into 3 is accompanied by a cleavage of the covalent PtSb bond present in 2 and formation of a longer and weaker Pt→Sb interaction in 3. These results show that this new Pt–Sb platform supports the fluoride‐induced metamorphosis of a stiboranyl X ligand into a stiborane Z ligand. Picture of (non)innocence: A chloride–fluoride exchange reaction leads to the metamorphosis of a stiboranyl X ligand into a stiborane Z ligand. This phenomenon, which illustrates the coordination non‐innocence of the antimony ligand, results from the cleavage of the covalent SbPt bond of 1 and formation of a longer and weaker Pt→Sb interaction in 2. This structural response is accompanied by a colorimetric one.
Bibliography:I.-O.K. and J.S.J. contributed equally to this work. Financial support from the Welch Foundation (A-1423), the National Science Foundation (CHE-1300371), Texas A&M University (Davidson Professorship), and the Laboratory for Molecular Simulation at Texas A&M University (software and computation resources) is gratefully acknowledged. We thank Lisa Pérez and Steve Silber for their help with DFT and 195Pt NMR studies, respectively.
ark:/67375/WNG-7XJG3KGS-G
Welch Foundation - No. A-1423
ArticleID:ANIE201309132
National Science Foundation - No. CHE-1300371
istex:239D8051CF3D20C781AD5EA32F4F567ECBA4400F
195
Pt NMR studies, respectively.
I.‐O.K. and J.S.J. contributed equally to this work. Financial support from the Welch Foundation (A‐1423), the National Science Foundation (CHE‐1300371), Texas A&M University (Davidson Professorship), and the Laboratory for Molecular Simulation at Texas A&M University (software and computation resources) is gratefully acknowledged. We thank Lisa Pérez and Steve Silber for their help with DFT and
National Science Foundation
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201309132