Crystal structure of [Zn(NHCH2(CH3)P(O)O−)Cl2] (α‐aminomethyl(methyl)phosphinic)zinc(II) dichloride

Two new tetraamine ligands, bis[N‐(2‐aminoethyl)aminomethyl]phosphinic acid (Hen2p) and bis[N‐(3‐aminopropyl)aminomethyl]phosphinic acid (Hpn2p), were synthesized from the corresponding diaminoalkanes and bis(chloromethyl)phosphinic acid. Their acid–base properties and complexation with Cu2+, Ni2+, and Zn2+ ions were studied by potentiometric titrations. Different chain lengths of the ligands result in significantly different coordination abilities. The five‐membered chelate ring of Hen2p leads to a higher stability of its complexes. In comparison with tetraamines having the same number of the bridging atoms separating the amino groups, the presence of the phosphinic acid moiety decreases the basicity of the amine groups, and consequently, the stability of their complexes. Several solid‐state structures were determined by X‐ray diffraction analysis. Four nitrogen atoms coordinate the Cu2+ or Zn2+ ion in a square‐planar fashion, whereas the phosphinic acid group is not coordinated or acts as a bridging unit between neighboring metal ions. The unexpectedly high stability of the Ni2+/Hpn2p complex can be explained by the possible presence of a tetramer in solution as was found in the solid state.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Aminoalkyl‐1,1‐bis(phosphinic acids): Stability, Acid–Base, and Coordination Properties

David

Procházková

Kotek

et al. 2014

Eur J Inorg Chem

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Four geminal bis(phosphinic acids), namely, aminomethylbis(H‐phosphinic acid) (H2L1) and 4‐aminobutyl‐1‐hydroxy‐1,1‐bis(R‐phosphinic acid) with R = H (H2L2), Me (H2L3) and CH2CH2COOH (H4L4), were studied. Their acid–base properties and coordination ability towards Cu2+, Ni2+ and Zn2+ ions were studied by potentiometry, UV/Vis spectroscopy and NMR spectroscopy. The amine group in H2L1 has a lower protonation constant (log Ka = 6.79) than those found for other studied bisphosphinates (log Ka = 10.75–11.05) with distant amine groups. The structure of [Ca(H2L2‐O,O′)(HL2‐O,O′)]Cl revealed an octahedral arrangement of the metal coordination sphere and a linear polymeric structure, which forms through eight‐membered Ca(–O–P–O–)2Ca rings. The structure of [Cu(HL3‐O,O′)2(H2O)]·5H2O shows two chelating bisphosphinate groups in an equatorial O4 environment. The structure of [Cu(H0.5L3‐O,O′)(NO3)0.5]·2.25H2O shows two different coordination environments, one is an elongated tetragonal pyramid, and the other is a trigonal bipyramid with a bidentate nitrate ion.

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Crystal structure of [Zn(NHCH₂(CH₃)P(O)O⁻)Cl₂] (α‐aminomethyl(methyl)phosphinic)zinc(II) dichloride

Cited by 12 publications

References 6 publications

ChemInform Abstract: CRYSTAL STRUCTURE OF (ZN(NH3+CH2)(CH3)P(O‐)CL2) (α‐AMINOMETHYL(METHYL)PHOSPHINIC ACID)ZINC (II) DICHLORIDE

ChemInform Abstract: CRYSTAL STRUCTURE OF (ZN(NH3+CH2)(CH3)P(O‐)CL2) (α‐AMINOMETHYL(METHYL)PHOSPHINIC ACID)ZINC (II) DICHLORIDE

Synthesis and Coordination Behavior of Symmetrical Tetraamine Phosphinic Acids

Aminoalkyl‐1,1‐bis(phosphinic acids): Stability, Acid–Base, and Coordination Properties

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