Universität zu Köln

Klare, Helge, Hanft, Sebastian, Neudoerfl, Joerg M., Schloerer, Nils E., Griesbeck, Axel and Goldfuss, Bernd ORCID: 0000-0002-1814-8818 (2014). Anion Recognition with Hydrogen-Bonding Cyclodiphosphazanes. Chem.-Eur. J., 20 (37). S. 11847 - 11856. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1521-3765

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Abstract

Modular cyclodiphosph(V)azanes are synthesised and their affinity for chloride and actetate anions were compared to those of a bisaryl urea derivative (1). The diamidocyclodiphosph(V)azanes cis-[{ArNHP(O)(mu-tBu)}(2)] [Ar=Ph (2) and Ar=m-(CF3)(2)Ph (3)] were synthesised by reaction of [{ClP(mu-NtBu)}(2)] (4) with the respective anilines and subsequent oxidation with H2O2. Phosphazanes 2 and 3 were obtained as the cis isomers and were characterised by multinuclear NMR spectroscopy, FTIR spectroscopy, HRMS and single-crystal X-ray diffraction. The cyclodiphosphazanes 2 and 3 readily co-crystallise with donor solvents such as MeOH, EtOH and DMSO through bidentate hydrogen bonding, as shown in the X-ray analyses. Cyclodiphosphazane 3 showed a remarkably high affinity (log[K]=5.42) for chloride compared with the bisaryl urea derivative 1 (log[K]=4.25). The affinities for acetate (AcO-) are in the same range (3: log[K]=6.72, 1: log[K]=6.91). Cyclodiphosphazane 2, which does not contain CF3 groups, exhibits weaker binding to chloride (log[K]=3.95) and acetate (log[K]=4.49). DFT computations and X-ray analyses indicate that a squaramide-like hydrogen-bond directionality and C-alpha-H interactions account for the efficiency of 3 as an anion receptor. The C-alpha-H groups stabilise the Z,Z-3 conformation, which is necessary for bidentate hydrogen bonding, as well as coordinating with the anion.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Klare, Helge UNSPECIFIED UNSPECIFIED UNSPECIFIED Hanft, Sebastian UNSPECIFIED UNSPECIFIED UNSPECIFIED Neudoerfl, Joerg M. UNSPECIFIED UNSPECIFIED UNSPECIFIED Schloerer, Nils E. UNSPECIFIED UNSPECIFIED UNSPECIFIED Griesbeck, Axel UNSPECIFIED UNSPECIFIED UNSPECIFIED Goldfuss, Bernd UNSPECIFIED orcid.org/0000-0002-1814-8818 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-428906
DOI:	10.1002/chem.201403013
Journal or Publication Title:	Chem.-Eur. J.
Volume:	20
Number:	37
Page Range:	S. 11847 - 11856
Date:	2014
Publisher:	WILEY-V C H VERLAG GMBH
Place of Publication:	WEINHEIM
ISSN:	1521-3765
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language MOLECULAR RECOGNITION; SQUARAMIDE DERIVATIVES; RECEPTORS; CRYSTAL; UREA; CATALYSTS; THIOUREA; GUEST; ACID; DFT Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/42890