TY - JOUR

T1 - Crystalline nickel(II) di-i-amyl dithiophosphate, [Ni{S2P(O-i-C5H11)2}2]

T2 - Preparation, structure, heteronuclear (13C, 31P) CP/MAS NMR spectra, and thermal behavior

AU - Korneeva, E. V.

AU - Larsson, A. C.

AU - Ivanov, A. V.

AU - Novikova, E. V.

AU - Smolentsev, A. I.

AU - Antzutkin, O. N.

PY - 2017/4/1

Y1 - 2017/4/1

N2 - The crystalline nickel(II) di-i-amyl) dithiophosphate (Dtph), [Ni{S2P(O-i-C5H11)2}2] (I) was isolated on a preparative scale and characterized by 13C, 31P MAS NMR, and X-ray diffraction (CIF file CCDC no. 1469369). The χ2-statistic diagrams were constructed from full 31P CP/MAS NMR spectra for calculating the 31P chemical shift anisotropy: δaniso = δzz–δiso and the asymmetry parameter η = (δyy–δxx)/(δzz–δiso). The key structural unit of I is the centrosymmetric [Ni{S2P(O-i-C5H11)2}2] molecule in which the nickel atom coordinates two Dtph ligands in the isobidentate fashion. In molecule I, each carbon, oxygen, and sulfur atom is statistically disordered over two sites with equal occupancies. However, the disorder does not affect nickel and phosphorus. These results were interpreted as the presence in I of two [Ni{S2P(O-i-C5H11)2}2] molecules rotated through 21.0(1)° (the angle between the [NiS4] chromophore planes) relative to each other around the bisecting P–Ni–P axis passing through both four-membered [NiS2P] rings. The two molecules occupy crystal lattice sites with equal probabilities. The thermal behavior of I was studied by simultaneous thermal analysis under argon. The course of the thermal destruction of the complex was established, nickel pyrophosphate (Ni2P2O7) was identified as the final product of thermal transformations.

AB - The crystalline nickel(II) di-i-amyl) dithiophosphate (Dtph), [Ni{S2P(O-i-C5H11)2}2] (I) was isolated on a preparative scale and characterized by 13C, 31P MAS NMR, and X-ray diffraction (CIF file CCDC no. 1469369). The χ2-statistic diagrams were constructed from full 31P CP/MAS NMR spectra for calculating the 31P chemical shift anisotropy: δaniso = δzz–δiso and the asymmetry parameter η = (δyy–δxx)/(δzz–δiso). The key structural unit of I is the centrosymmetric [Ni{S2P(O-i-C5H11)2}2] molecule in which the nickel atom coordinates two Dtph ligands in the isobidentate fashion. In molecule I, each carbon, oxygen, and sulfur atom is statistically disordered over two sites with equal occupancies. However, the disorder does not affect nickel and phosphorus. These results were interpreted as the presence in I of two [Ni{S2P(O-i-C5H11)2}2] molecules rotated through 21.0(1)° (the angle between the [NiS4] chromophore planes) relative to each other around the bisecting P–Ni–P axis passing through both four-membered [NiS2P] rings. The two molecules occupy crystal lattice sites with equal probabilities. The thermal behavior of I was studied by simultaneous thermal analysis under argon. The course of the thermal destruction of the complex was established, nickel pyrophosphate (Ni2P2O7) was identified as the final product of thermal transformations.

KW - C and P CP/MAS NMR spectroscopy

KW - P chemical shift anisotropy

KW - molecular structures

KW - nickel(II) dialkyl dithiophosphate complexes

KW - structural disorder

KW - thermal transformations of nickel(II) dithiophosphates

KW - SQUARE-PLANAR

KW - MOLECULAR-STRUCTURE

KW - PHOSPHORODITHIOATO)NICKEL(II)

KW - COMPLEXES

KW - REDETERMINATION

KW - X-RAY-DIFFRACTION

KW - SUPRAMOLECULAR SELF-ORGANIZATION

KW - CHEMICAL-SHIFT ANISOTROPY

KW - C-13 and P-31 CP/MAS NMR spectroscopy

KW - SPECTROSCOPY

KW - P-31 chemical shift anisotropy

KW - SOLIDS

UR - http://www.scopus.com/inward/record.url?scp=85018504670&partnerID=8YFLogxK

U2 - 10.1134/S1070328417040030

DO - 10.1134/S1070328417040030

M3 - Article

AN - SCOPUS:85018504670

VL - 43

SP - 223

EP - 231

JO - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya

JF - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya

SN - 1070-3284

IS - 4

ER -