New Lanthanide Alkynylamidinates and Diiminophosphinates
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-propiolamidinate...
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MDPI AG
2015-11-01
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| Series: | Inorganics |
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| Online Access: | http://www.mdpi.com/2304-6740/3/4/429 |
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| author | Farid M. Sroor Cristian G. Hrib Frank T. Edelmann |
| author_facet | Farid M. Sroor Cristian G. Hrib Frank T. Edelmann |
| author_sort | Farid M. Sroor |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-04-12T06:34:35Z |
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| last_indexed | 2024-04-12T06:34:35Z |
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| spelling | doaj.art-677e755ac90d4dedaa525ccfcfcc0fe12022-12-22T03:43:54ZengMDPI AGInorganics2304-67402015-11-013442944710.3390/inorganics3040429inorganics3040429New Lanthanide Alkynylamidinates and DiiminophosphinatesFarid M. Sroor0Cristian G. Hrib1Frank T. Edelmann2Organometallic and Organometalloid Chemistry Department, National Research Centre, 12622 Cairo, EgyptChemisches Institut der Otto-von-Guericke-Universität Magdeburg, 39106 Magdeburg, GermanyChemisches Institut der Otto-von-Guericke-Universität Magdeburg, 39106 Magdeburg, GermanyThis 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.http://www.mdpi.com/2304-6740/3/4/429amidinatealkynylamidinatediiminophosphinatelithiumlanthanide complexescrystal structure |
| spellingShingle | Farid M. Sroor Cristian G. Hrib Frank T. Edelmann New Lanthanide Alkynylamidinates and Diiminophosphinates Inorganics amidinate alkynylamidinate diiminophosphinate lithium lanthanide complexes crystal structure |
| title | New Lanthanide Alkynylamidinates and Diiminophosphinates |
| title_full | New Lanthanide Alkynylamidinates and Diiminophosphinates |
| title_fullStr | New Lanthanide Alkynylamidinates and Diiminophosphinates |
| title_full_unstemmed | New Lanthanide Alkynylamidinates and Diiminophosphinates |
| title_short | New Lanthanide Alkynylamidinates and Diiminophosphinates |
| title_sort | new lanthanide alkynylamidinates and diiminophosphinates |
| topic | amidinate alkynylamidinate diiminophosphinate lithium lanthanide complexes crystal structure |
| url | http://www.mdpi.com/2304-6740/3/4/429 |
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