Synthesis, Structure, and Reactivity of Ru^II Complexes with Trimethylsilylethinylamidinate Ligands

Abstract

The mononuclear amidinate complexes [(η 6 -cymene)-Ru-Cl(1a)] (2) and [(η 6 -C 6 H 6 )RuCl(1b)] (3), with the trimethylsilyl-ethinylamidinate ligands [Me 3 SiCϵCC(N-c-C 6 H 11 ) 2 ] -(1a -) and [Me 3 SiCϵCC(N-i-C 3 H 7 ) 2 ] -(1b -) were synthesized in high yields by salt metathesis. In addition, the related phosphane complexes [(η 5 -C 5 H 5 )Ru(PPh 3 )(1b)] (4a) [(η 5 -C 5

Lithium‐cyclopropylethinylamidinates

“…The new lithiumcyclopropylethinylamidinates 2a, b, c and 3a, b, c have been fully characterized by spectroscopic methods, elemental analyses, and single‐crystal X‐ray diffraction studies of the THF adducts 2b and 3b . Especially notable are the 13 C NMR spectra, which show a significant difference to the 13 C NMR spectroscopic data of the recently described trimethylsilylethinylamidinates Li[Me 3 Si–C≡C–C(N i Pr) 2 ] and Li[Me 3 Si–C≡C–C(NCy) 2 ] 8. For example, the 13 C shifts of the acetylenic carbon atoms in Li[Me 3 Si–C≡C–C(NCy) 2 ] have been reported to appear at δ = 98.5 and 96.5 ppm.…”

“…The use of diethyl ether as solvent proved to be favorable, because under these conditions Li[Me 3 Si–C≡C–C(N i Pr) 2 ] and Li[Me 3 Si–C≡C–C(NCy) 2 ] could be obtained in crystalline form as colorless salts. X‐ray diffraction studies of the diethyl ether adducts revealed typical dimeric structures with the amidinate ligands serving as a chelate with one lithium ion, whereas one of the nitrogen donor atoms additionally bridges to the second lithium atom 8…”

Lanthanide(III)-bis(cyclopropylethinylamidinates): Synthesis, structure, and catalytic activity

“…Following a report that lithium-trimethylsilylethinylamidinates are readily available from the reaction between either N,N 0 -diisopropylcarbodiimide or N,N 0 -dicyclohexylcarbodiimide and lithiumtrimethylsilylacetylide in diethyl ether [8], we recently described the synthesis and full characterization of a series of lithiumcyclopropylethinylamidinates [9]. These precursors are readily available on a large scale using commercially available starting materials.…”

“…Supplementary data CCDC-1001399 (2a), 1001400 (2b), 1001401 (2c), 1001403 (3), 1001402 (8), and 1001404 (9) contain the supplementary crystallographic data for this Paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.…”

Five different types of η8-cyclooctatetraenyl-lanthanide half-sandwich complexes from one ligand set, including a “giant neodymium wheel”

“…1 In the case of rare-earth metals, mono-, di-and trisubstituted lanthanide amidinate and guanidinate complexes are all accessible, just like the mono-, di-and tricyclopentadienyl complexes. 7 9 In the course of our ongoing investigation of lanthanide amidinates we recently initiated a study of alkynylamidinates derived from cyclopropylacetylene. 25 years, lanthanide amidinates have undergone an impressive transformation from laboratory curiosities to highly active homogeneous catalysts as well as valuable precursors in materials science.…”