Universität zu Köln

Wolf, Florian F., Neudoerfl, Joerg-M. and Goldfuss, Bernd ORCID: 0000-0002-1814-8818 (2018). Hydrogen-bonding cyclodiphosphazanes: superior effects of 3,5-(CF3)(2)-substitution in anion-recognition and counter-ion catalysis. New J. Chem., 42 (7). S. 4854 - 4871. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1369-9261

Full text not available from this repository.

Abstract

New HB-cyclodiphosph(v)azanes with a variety of structural modifications, e.g. unsymmetrical substitution of phosphorus atoms with sulfur and oxygen atoms as well as either phenyl- (O(=P)/S(=P)-13) or 3,5-(CF3)(2)-C6H3-substitution (O(=P)/S(=P)-14) and 3,5-F2C6H3-substituted cyclodiphosph(v)azanes with either oxygen (O(=P)-15) or sulfur (S(=P)-16) substitution at the phosphorus atoms, are synthesized. These new systems are employed together with sulfur substituted cyclodiphosph(v)azanes with phenyl- (11) and 3,5-(CF3)(2)-C6H3-substitution (12) in recognitions of chloride and acetate anions. These HB-systems are compared to the previously established reference systems, i.e. cyclodiphosph(v)azanes (4, 5), thiourea (20) and squaramides (21, 22). Modifications of the chalcogen atom in the cyclodiphosph(v)azane moieties from oxygen (O(=P)-5) to sulfur (O(=P)/S(=P)-14, S(=P)-12) reveal a decrease in anion binding capabilities. 3,5-(CF3)(2)-C6H3 substituted O(=P)-cyclodiphosph(v)azane 5 exhibits the strongest anion binding effect (chloride: log[K] 5.91, log[K] acetate: 6.06) in acetonitrile, surpassing even the established thiourea 20 (chloride: log[K] 4.30, log[K] acetate: 5.47) as well as squaramides 21 (chloride: log[K] 4.92, acetate: log[K] 4.24) and 22 (chloride: log[K] 5.13, acetate: log[K] 5.37). Computational studies confirm 3,5-(CF3)(2)-C6H3 substituted 5 to be the strongest here studied anion-binding cyclodiphosph(v)azane with computed binding energies Delta G(in-out center dot Cl) of -21.1 kcal mol(-1) and Delta G(in-out center dot OAc) of -14.3 kcal mol(-1), surpassing thiourea 20 (Delta G(in-out center dot)Cl = -19.10 kcal mol(-1), Delta G(in-out center dot)OAc = -13.81 kcal mol(-1)). The catalytic efficiency of 3,5-(CF3)(2)-C6H3 substituted cyclodiphosph(v)azane 5 is examined in a N-acyl-Mannich reaction, showing a significantly higher reactivity (up to 45% yield) compared to the alternative hydrogen-bonding catalyst di(1-naphthyl)silanediol 28. In all these applications, the superiority of the 3,5-(CF3)(2)-C6H3 substitution pattern in combination with O(=P)-groups in the cyclodiphosph(v)azane scaffold is apparent.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Wolf, Florian F. UNSPECIFIED UNSPECIFIED UNSPECIFIED Neudoerfl, Joerg-M. UNSPECIFIED UNSPECIFIED UNSPECIFIED Goldfuss, Bernd UNSPECIFIED orcid.org/0000-0002-1814-8818 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-189588
DOI:	10.1039/c7nj04660j
Journal or Publication Title:	New J. Chem.
Volume:	42
Number:	7
Page Range:	S. 4854 - 4871
Date:	2018
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	1369-9261
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 BINDING CATALYSIS; E,Z CONFORMATION; THIOUREA; DENSITY; SQUARAMIDE; SPECTROSCOPY; DESIGN; DEAROMATIZATION; DERIVATIVES; RESOLUTION Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/18958