New Lanthanide Alkynylamidinates and Diiminophosphinates

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