Heteroarylphosphorus compounds: Nickel(II) and cobalt(II) complexes of thienylphosphines |
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| Affiliation: | 1. Department of Pure and Industrial Chemistry, University of Nigeria, Nsukka, 410001, Nigeria;2. Department of Chemical and Process Engineering, Jubail Industrial College, Jubail Industrial City 31961, Saudi Arabia;3. Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, Réduit 80837, Mauritius;4. Department of Applied Chemistry, University of Johannesburg, Doornfontein Campus, Johannesburg 2028, South Africa;5. Technische Universität, Fakultät für Chemie und Chemische Biologie, D-44221 Dortmund, Germany;6. Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, Samsun 55139, Turkey;1. Department of Chemistry, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh;2. Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK;3. Department of Chemistry, University of North Texas, 1155 Union Circle, Box 305070, Denton, TX 76203, USA;1. Department of Chemistry and Biochemistry, MSC 4501, James Madison University, Harrisonburg, VA 22807, USA;2. Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA |
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| Abstract: | Complexes of a series of tertiary phosphines bearing 2-thienyl groups with nickel(II) and cobalt(II) halides and thiocyanates have been prepared and their magnetic and spectroscopic properties are presented. The nickel(II) halide and cobalt(II) halide and thiocyanate complexes have a distorted tetrahedral structure, whereas the nickel(II) thiocyanate complexes are square planar. Consideration of the spectroscopic data for the tetrahedral nickel(II) halide complexes of the thienylphosphines indicates that a 2-thienyl substituent is more electron-releasing towards phosphorus than is a phenyl group when the phosphorus is coordinated to the metal, suggesting that in this situation effects of pπ−dπ interactions between the heterocyclic ring system and phosphorus may be significant in influencing the donor properties of the phosphine. Calculation of the Racah parameters for the nickel(II) complexes indicates that the nephelauxetic effects of the thienylphosphines are different from those of triphenylphosphine and that there is a greater degree of covalency in the metal-ligand bond in the case of the thienylphosphines. |
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