Synthesis and complexation of N,N-Bis(O-diethylhydroxyphosphorylmethyl)-N-butylamine

Article abstract of DOI:10.1080/10426507.2018.1539998

The acid-base and complexing properties of N,N-bis(O-diethylhydroxyphosphorylmethyl)-N-butylamine (H₃L) with divalent metals were investigated in aqueous solution via the potentiometric titration method. The formation of 1:1 species has been established. The structure of complex N,N-bis(O-diethylhydroxyphosphorylmethyl)-N-butylamine with copper(II) was determined using an X-ray diffraction method.

Full text of DOI:10.1080/10426507.2018.1539998

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: https://www.tandfonline.com/loi/gpss20
Synthesis and complexation of N,N-Bis(O-
diethylhydroxyphosphorylmethyl)-N-butylamine
Rafael A. Cherkasov, Igor D. Shurygin, Airat R. Garifzyanov, Ildar I.
Mirzayanov, Aynaz Z. Gaynullin, Kamil A. Ivshin & Olga N. Kataeva
To cite this article: Rafael A. Cherkasov, Igor D. Shurygin, Airat R. Garifzyanov, Ildar I.
Mirzayanov, Aynaz Z. Gaynullin, Kamil A. Ivshin & Olga N. Kataeva (2018): Synthesis and
complexation of N,N-Bis(O-diethylhydroxyphosphorylmethyl)-N-butylamine, Phosphorus, Sulfur,
and Silicon and the Related Elements, DOI: 10.1080/10426507.2018.1539998
To link to this article: https://doi.org/10.1080/10426507.2018.1539998
Published online: 10 Dec 2018.
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2018.1539998
SHORT COMMUNICATION
Synthesis and complexation of N,N-Bis(O-diethylhydroxyphosphorylmethyl)-
N-butylamine
Rafael A. Cherkasova , Igor D. Shurygina, Airat R. Garifzyanova , Ildar I. Mirzayanova, Aynaz Z. Gaynullina,
Kamil A. Ivshina , and Olga N. Kataevab
b
aA.M. Butlerov Institute of Chemistry, Kazan federal university, Kazan, Russia; Arbuzov Institute of Organic and Physical Chemistry, Kazan
Scientific Center, Russian Academy of Sciences, Kazan Russia
ABSTRACT
ARTICLE HISTORY
Received 21 September 2018
Accepted 11 October 2018
The acid-base and complexing properties of N,N-bis(O-diethylhydroxyphosphorylmethyl)-N-butyl-
amine (H3L) with divalent metals were investigated in aqueous solution via the potentiometric
titration method. The formation of 1:1 species has been established. The structure of complex
N,N-bis(O-diethylhydroxyphosphorylmethyl)-N-butylamine with copper(II) was determined using an
X-ray diffraction method.
KEYWORDS
Acid-base properties;
aminophosphonates; stabil-
ity constants; complexation
GRAPHICAL ABSTRACT
Organophosphorus chelating agents are widely used in
The mononuclear complex species MLꢀ are predominant
many applications. Herein we report our investigations of at the neutral and alkaline solutions, while MHL species
complexing properties of N,N-bis(O-diethylhydroxyphos- occur at the acidic solutions. Complexes’ destruction begins
phorylmethyl)-N-butylamine (H3L).
Potassium salt of H3L was synthesized according to the five-membered rings.
following Scheme 1: The complex
with nitrogen atom protonation leading to the opening of
N,N-bis(O-diethylhydroxyphosphoryl-
The dissociation constants (hR1 and hR2 for phosphonic methyl)-N-butylamine with copper(II) (Figure 1 was synthe-
acid groups, hR3 for amino group) of H3L having the values sized by addition of a copper(II) nitrate solution (5 mL
hR1 1.05, hR2 1.20, and hR3 7.74 were determined via the (0.1 mol/L)) to a H3L (5 mL (0.1 mol/L)) solution. The mix-
potentiometric titration. During the complexation research ture was kept in an open vessel at room temperature
of H3L with divalent metal’s ions in aqueous solution at the for 2 months.
pH values between 1.5 and 9 at a molar ratio of metal to lig-
This study was performed under financial support by the
and is 1:1, there are only MHL and MLꢀ complexes. The state subsidy allocated for Kazan Federal University for its
stability constants are presented in Table 1.
competitive growth.
Scheme 1. Synthesis of N,N-bis(O-diethylhydroxyphosphorylmethyl)-N-butylamine.
Table 1. The stability constants of H3L complexes with divalent metal’s ions.
2+
2+
2+
2+
2+
2+
CO
2+
2+
CU
2+
2+
CD
LGΒ
MG
CA
SR
BA
MN
NI
ZN
MHL
ML¯
1.31
1.71
1.50
1.85
0.58
1.02
0.97
1.17
1.25
2.76
1.99
3.47
1.79
3.50
1.59
5.98
1.70
3.76
0.90
3.96
CONTACT Igor D. Shurygin
idshurygin@gmail.com
ß 2018 Taylor & Francis Group, LLC

2
R. A. CHERKASOV ET AL.
Figure 1. Crystal structure of complex N,N-bis(O-diethylhydroxyphosphorylmethyl)-N-butylamine with copper(II).
The ionic strength of all solutions was adjusted to 0.2 mol/L
(KNO3) and the temperature was maintained at 25.0 0.1 ꢁC.
The pH values were measured with an Expert-001-2 instru-
ment equipped with an ES-10603 glass electrode.
Data set for single crystal of C10H27CuNO8P2ꢂ3H2O was col-
lected on a Bruker Smart APEX II CCD diffractometer with
graphite-monochromated Mo-Ka radiation (k ¼ 0.71073 Å) at
T¼ 120(2) K. Crystal size 0.511 ꢃ 0.405 ꢃ 0.273 mm3. Programs
used: data collection APEX3,[1] data reduction SAINT,[2] structure
solution SHELXS,[3] structure refinement by full-matrix least-
squares against F2 using SHELXL.[3] CCDC 1868817 contains the
supplementary crystallographic data for this paper.
ORCID
Rafael A. Cherkasov
Airat R. Garifzyanov
Kamil A. Ivshin
http://orcid.org/0000-0001-8604-9953
http://orcid.org/0000-0002-6613-8788
http://orcid.org/0000-0002-9720-7977
http://orcid.org/0000-0002-9763-5947
Olga N. Kataeva
References
[1] Bruker. APEX3 Crystallography Software Suite, Bruker AXS,
Inc., Madison, WI, USA, 2016.
[2] Bruker. SAINT Crystallography Software Suite, Bruker AXS,
Inc., Madison, WI, USA, 2016.
[3] Sheldrick, G. M. A short history of SHELX. Acta Crystallogr. A
Found. Adv. 2008, 64, 112–122.