Crystalline nickel(II) di-i-amyl dithiophosphate, [Ni{S2P(O-i-C5H11)2}2]: Preparation, structure, heteronuclear (13C, 31P) CP/MAS NMR spectra, and thermal behavior

• Published in: Russian journal of coordination chemistry Vol. 43; no. 4; pp. 223 - 231
• Main Authors: Korneeva, E. V., Larsson, A.-C., Ivanov, A. V., Novikova, E. V., Smolentsev, A. I., Antzutkin, O. N.
• Format: Journal Article
• Language: English
• Published: Moscow Pleiades Publishing 01.04.2017; Springer Nature B.V
• Subjects: Anisotropy; Carbon 13; Chemistry; Chemistry and Materials Science; Chemistry of Interfaces; Gränsytors kemi; Inorganic Chemistry; Ligands; Physical Chemistry; P CP/MAS NMR spectroscopy; P chemical shift anisotropy; molecular structures; C and; structural disorder; nickel(II) dialkyl dithiophosphate complexes; thermal transformations of nickel(II) dithiophosphates
• ISSN: 1070-3284; 1608-3318; 1608-3318
• DOI: 10.1134/S1070328417040030

The crystalline nickel(II) di- i -amyl) dithiophosphate (Dtph), [Ni{S 2 P(O- i -C 5 H 11 ) 2 } 2 ] ( I ) was isolated on a preparative scale and characterized by 13 C, 31 P MAS NMR, and X-ray diffraction (CIF file CCDC no. 1469369). The χ 2 -statistic diagrams were constructed from full 31 P CP/MAS NMR spectra for calculating the 31 P chemical shift anisotropy: δ aniso = δ zz –δ iso and the asymmetry parameter η = (δ yy –δ xx )/(δ zz –δ iso ). The key structural unit of I is the centrosymmetric [Ni{S 2 P(O- i -C 5 H 11 ) 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{S 2 P(O- i -C 5 H 11 ) 2 } 2 ] molecules rotated through 21.0(1)° (the angle between the [NiS 4 ] chromophore planes) relative to each other around the bisecting P–Ni–P axis passing through both four-membered [NiS 2 P] 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 (Ni 2 P 2 O 7 ) was identified as the final product of thermal transformations.