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Inorganics 2015, 3(4), 429-447; doi:10.3390/inorganics3040429

New Lanthanide Alkynylamidinates and Diiminophosphinates

1
Organometallic and Organometalloid Chemistry Department, National Research Centre, 12622 Cairo, Egypt
2
Chemisches Institut der Otto-von-Guericke-Universität Magdeburg, 39106 Magdeburg, Germany
*
Author to whom correspondence should be addressed.
Academic Editors: Stephen Mansell and Steve Liddle
Received: 7 October 2015 / Revised: 23 October 2015 / Accepted: 27 October 2015 / Published: 5 November 2015
(This article belongs to the Special Issue Rare Earth and Actinide Complexes)
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Abstract

This contribution reports the synthesis and structural characterization of several new lithium and lanthanide alkynylamidinate complexes. Treatment of PhC≡CLi with N,N′-diorganocarbodiimides, R–N=C=N–R (R = iPr, Cy (cyclohexyl)), in THF or diethyl ether solution afforded the lithium-propiolamidinates Li[Ph–C≡C–C(NCy)2] S (1: R = iPr, S = THF; 2: R = Cy, S = THF; 3: R = Cy, S = Et2O). Single-crystal X-ray diffraction studies of 1 and 2 showed the presence of typical ladder-type dimeric structures in the solid state. Reactions of anhydrous LnCl3 (Ln = Ce, Nd, Sm or Ho) with 2 in a 1:3 molar ratio in THF afforded a series of new homoleptic lanthanide tris(propiolamidinate) complexes, [Ph–C≡C–C(NCy)2]3Ln (4: Ln = Ce; 5: Ln = Nd; 6: Ln = Sm; 7: Ln = Ho). The products were isolated in moderate to high yields (61%–89%) as brightly colored, crystalline solids. The chloro-functional neodymium(III) bis(cyclopropylethynylamidinate) complex [{c-C3H5–C≡C–C(NiPr)2}2Ln(µ-Cl)(THF)]2 (8) was prepared from NdCl3 and two equiv. of Li[c-C3H5–C≡C–C(NiPr)2] in THF and structurally characterized. A new monomeric Ce(III)-diiminophosphinate complex, [Ph2P(NSiMe3)2]2Ce(µ-Cl)2Li(THF)2 (9), has also been synthesized in a similar manner from CeCl3 and two equiv. of Li[Ph2P(NSiMe3)2]. Structurally, this complex resembles the well-known “ate” complexes (C5Me5)2Ln(µ-Cl)2Li(THF)2. Attempts to oxidize compound 9 using trityl chloride or phenyliodine(III) dichloride did not lead to an isolable cerium(IV) species. View Full-Text
Keywords: amidinate; alkynylamidinate; diiminophosphinate; lithium; lanthanide complexes; crystal structure amidinate; alkynylamidinate; diiminophosphinate; lithium; lanthanide complexes; crystal structure
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Sroor, F.M.; Hrib, C.G.; Edelmann, F.T. New Lanthanide Alkynylamidinates and Diiminophosphinates. Inorganics 2015, 3, 429-447.

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