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Statements

Subject Item
n2:RIV%2F00216208%3A11310%2F13%3A10139594%21RIV14-GA0-11310___
rdf:type
n9:Vysledek skos:Concept
rdfs:seeAlso
http://dx.doi.org/10.1039/c2dt32045b
dcterms:description
Three symmetrical methylene-bis[(aminomethyl)phosphinic acids] bearing different substituents on the central carbon atom, (NH2CH2) PO2H-C(R-1)(R-2)-PO2H(CH2NH2) where R-1 = OH, R-2 = Me (H2L1), R-1 = OH, R-2 = Ph (H2L2) and R-1, R-2 = H (H2L3), were synthesized. Acid-base and complexing properties of the ligands were studied in solution as well as in the solid state. The ligands show unusually high basicity of the nitrogen atoms (log K-1 = 9.5-10, log K-2 = 8.5-9) if compared with simple (aminomethyl) phosphinic acids and, consequently, high stability constants of the complexes with studied divalent metal ions. The study showed the important role of the hydroxo group attached to the central carbon atom of the geminal bis(phosphinate) moiety. Deprotonation of the hydroxo group yields the alcoholate anion which tends to play the role of a bridging ligand and induces formation of polynuclear complexes. Solid-state structures of complexes [H2N=C(NH2)(2)][Cu-2(H-1L2)(2)]CO3 center dot 10H(2)O and Li-2[Co-4(H-1L1)(3)(OH)]center dot 17.5H(2)O were determined by X-ray diffraction. The complexes show unexpected geometries forming dinuclear and cubane-like structures, respectively. The dinuclear copper(II) complex contains a bridging mu(2)-alcoholate group with the O--P(=O)-CH2-NH2 fragments of each ligand molecule chelated to the different central ion. In the cubane cobalt(II) complex, one mu(3)-hydroxide and three mu(3)-alcoholate anions are located in the cube vertices and both phosphinate groups of one ligand molecule are chelating the same cobalt(II) ion while each of its amino groups are bound to different neighbouring metal ions. All such three metal ions are bridged by the alcoholate group of a given ligand. Three symmetrical methylene-bis[(aminomethyl)phosphinic acids] bearing different substituents on the central carbon atom, (NH2CH2) PO2H-C(R-1)(R-2)-PO2H(CH2NH2) where R-1 = OH, R-2 = Me (H2L1), R-1 = OH, R-2 = Ph (H2L2) and R-1, R-2 = H (H2L3), were synthesized. Acid-base and complexing properties of the ligands were studied in solution as well as in the solid state. The ligands show unusually high basicity of the nitrogen atoms (log K-1 = 9.5-10, log K-2 = 8.5-9) if compared with simple (aminomethyl) phosphinic acids and, consequently, high stability constants of the complexes with studied divalent metal ions. The study showed the important role of the hydroxo group attached to the central carbon atom of the geminal bis(phosphinate) moiety. Deprotonation of the hydroxo group yields the alcoholate anion which tends to play the role of a bridging ligand and induces formation of polynuclear complexes. Solid-state structures of complexes [H2N=C(NH2)(2)][Cu-2(H-1L2)(2)]CO3 center dot 10H(2)O and Li-2[Co-4(H-1L1)(3)(OH)]center dot 17.5H(2)O were determined by X-ray diffraction. The complexes show unexpected geometries forming dinuclear and cubane-like structures, respectively. The dinuclear copper(II) complex contains a bridging mu(2)-alcoholate group with the O--P(=O)-CH2-NH2 fragments of each ligand molecule chelated to the different central ion. In the cubane cobalt(II) complex, one mu(3)-hydroxide and three mu(3)-alcoholate anions are located in the cube vertices and both phosphinate groups of one ligand molecule are chelating the same cobalt(II) ion while each of its amino groups are bound to different neighbouring metal ions. All such three metal ions are bridged by the alcoholate group of a given ligand.
dcterms:title
Methylene-bis[(aminomethyl)phosphinic acids]: synthesis, acid-base and coordination properties Methylene-bis[(aminomethyl)phosphinic acids]: synthesis, acid-base and coordination properties
skos:prefLabel
Methylene-bis[(aminomethyl)phosphinic acids]: synthesis, acid-base and coordination properties Methylene-bis[(aminomethyl)phosphinic acids]: synthesis, acid-base and coordination properties
skos:notation
RIV/00216208:11310/13:10139594!RIV14-GA0-11310___
n9:predkladatel
n10:orjk%3A11310
n3:aktivita
n17:Z n17:S n17:P n17:I
n3:aktivity
I, P(GPP207/10/P153), S, Z(MSM0021620857)
n3:cisloPeriodika
7
n3:dodaniDat
n20:2014
n3:domaciTvurceVysledku
n4:9417850 n4:9767878 n4:5386381 n4:8438455 n4:3062228 n4:3978877 n4:9695656
n3:druhVysledku
n19:J
n3:duvernostUdaju
n16:S
n3:entitaPredkladatele
n22:predkladatel
n3:idSjednocenehoVysledku
87659
n3:idVysledku
RIV/00216208:11310/13:10139594
n3:jazykVysledku
n7:eng
n3:klicovaSlova
state; ligand; analogs; pcp(2-); complexes; phosphinic acid; aqueous-solution; structural-characterization; crystal-structures; inorganic-organic hybrids
n3:klicoveSlovo
n6:complexes n6:crystal-structures n6:structural-characterization n6:inorganic-organic%20hybrids n6:ligand n6:aqueous-solution n6:state n6:pcp%282-%29 n6:analogs n6:phosphinic%20acid
n3:kodStatuVydavatele
GB - Spojené království Velké Británie a Severního Irska
n3:kontrolniKodProRIV
[20F014D04427]
n3:nazevZdroje
Dalton Transactions
n3:obor
n14:CA
n3:pocetDomacichTvurcuVysledku
7
n3:pocetTvurcuVysledku
7
n3:projekt
n21:GPP207%2F10%2FP153
n3:rokUplatneniVysledku
n20:2013
n3:svazekPeriodika
42
n3:tvurceVysledku
David, Tomáš Lukeš, Ivan Hermann, Petr Procházková, Soňa Kubíček, Vojtěch Havlíčková, Jana Kotek, Jan
n3:wos
000313804200013
n3:zamer
n11:MSM0021620857
s:issn
1477-9226
s:numberOfPages
9
n5:doi
10.1039/c2dt32045b
n18:organizacniJednotka
11310