Das, P. N. Mohan

Hagele, G.

Kuchen, W.

English

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COMMUNICATIONS19. SCHWARTZ, M. E. & SWITALSKI, J. D., J. chem, Phys.,57 (1972), 4125.20. FROST, A. A., J. chem, Phys., 47 (1967), 3707.21. CHRISTOFFERSEN, R. E., SPANGLER, D., HALL, G. G. &MAGGIORA, G. M., J. Am. chem. Soc., 95 (1973), 8526.22. Obtained from QCPE, Chemistry Department, IndianaUniversity, Bloomington, Indiana 47401, USA.23. AMOS, A. T. & YOFFE, J. A., Chem, Phys. LeU., 31(1975), 57.24. AMOS, A. T. & YOFFE, J. A., cu«. Phys. Lett., 31(1975), 53.25. CHU, S. Y. & FROST, A. A., J. chem. Phys., 54 (1971), 760.26. FROST, A. A. & ROUSE, R. A., J. Am. chem, Soc., 90(1968), 1965.27. PAULING, L., The nature of the chemical bond (CornellUniversity Press), 1960.28. MOCCIA, R., J. chem, Phys., 40 (1964), 2164, 2176, 2186.Strong SolventChemical ShiftDependence ofin Lanthanide[(CH3);!PSJ3LnPhosphorusComplexesG. HAGELE, W. KUCHEN & P. N. MOHAN DASInstitut fur Anorganische und StrukturchemieUniversitat Dusseldorf, Universitatsstrasse 14000 Diisseldorf, 'West GermanyReceived 13 December 1976; accepted 27 December 1976The IH and IH(31P) NMR spectra of the paramag-netic complexes LnL3 [Ln= Pr(III), Nd(III), Eu(III),L=(CH3)2PS2] are found to be strongly solvent de-pendent. Solutions in acetone-d. exhibit greater haH-widths in P-CH3 doublet and larger lip values than thecorresponding solutions in methanol-d •.REACTIONS between stoichiometric amountsof lanthanide ions and the sodium salt ofdimethyldithiophosphinic acid (CH,')2P(S)SNa.2Hpin ethanol medium gave the octahedral complexesof the type (1)1.[(CH3).P /S'\...]3L-l"'s/ILn=La(III), Pr(III), Nd(III), Eu(III), Sm(III)2LHzTMS TMS TMSA 8 cFig. 1 - 60 MHz NMR spectrum for protons in[(CH3),PS')]3Pr [40 mg complex dissolved in 0·4 ml of solvents:CD,COCD. = A; CD3COCD,/CD30D (1: 1) = B; andCD30D=C]It is found that the 60 MHz IH and IH(31P) NMRspectra of the paramagnetic Pr(III), Nd(III) andEu(III) complexes are strongly solvent dependent.Solutions of I in acetone-a, exhibited greaterhalf-widths in P-CH3 doublet lines and larger apvalues than in methanol-a, (see Fig. 1). An unusualstrong sensitivity of ap in I towards change of thesolvent is observed. ap values were observed inthe wide range of about 100 ppm widths (see Table1). As we were able to prepare well-defined di-adducts, LnL3.2B of some complexes (I) (e.g. Ln=Pr(III); L= (CHa)2PS2; B=CHaOH, CsHsN) asstable solid compounds, we assume that thecoordination number six in I is expanded to eightin the solutions of the above-mentioned solvents.We suggest that the magnitude of the extremelystrong shift in ap and the change in the spectralhalf-widths may be in correlation with the solventdonor properties. Therefore, we intend to usethe paramagnetic complexes (I) in particular[(CH3hPS213Pr for systematic studies of their inter-actions with a wide variety of donor solvents.References1. MOHAN DAS, P. N., KUCHEN, W., KECK, H. & HAGELE, G.,J. inorg. nuci. Chem., (in press).TABLE I-SOLVENT DEPENDENT CHEMICAL SHIFTS OF PHOSPHORUS, PROTON AND SPECTRAL HALF-WIDTHS OF P-CH3 DOUBLETSCompound CD3COCD, CD,ODOP oIl tJ.vl/2 op OH tJ.vlj2LH 2-117 0·5 +50·9 2'083 0·5LaL3 +52·2 2·000 1PrL3 +19·2 1-167 10 -51-4 -0·242 3NdL3 -26,7 2·767 15 -58,4 1·558 1SmL3 +57·6 1·783 10 +53·7 1·792 6EuL3 +51·2 -0·222 3·5 -24,3 1·735 1·5oP= phosphorus chemical shift calc. vs H.PO. 85% (ppm).OH= proton chemical shift vs TMS (ppm).tJ.vI/2 = spectral half-width of P-CH3 doublets (Hz).LH = (CH,hPS2H.147

Strong Solvent Chemical Shift Dependence of in Lanthanide [(CH3)2PS2]3Ln Phosphorus Complexes

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Strong Solvent Chemical Shift Dependence of in Lanthanide [(CH3)2PS2]3Ln Phosphorus Complexes

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