Komplexe der d⁸‐Edelmetalle sowie des Mangans und Rheniums mit Tricyan‐ und Tris(äthoxycarbonyl)methanid‐Liganden

Reaction Mechanism of the C⋮N Triple Bond Cleavage ofβ-Ketonitriles on a Molybdenum(0) Center1

“…The IR spectra of (nitrido)(nitrile-enolato) complexes 4 showed absorptions with medium intensities at 974−990 cm -1 characteristic of the Mo⋮N bond. , The ν (C⋮N) band due to the coordinated cyano group in 4 appeared at 2141−2168 cm -1 . This value is comparable to those reported for the N-bound cyanoenolato (2110−2200 cm -1 ) 39-42 or keteniminato complexes (2120−2190 cm -1 ). − Two absorptions observed at 1405−1422 and 1509−1592 cm -1 are assignable to the enolate group. The 1 H NMR spectra of 4b − g and 4j displayed a singlet at δ 3.38−3.93 with the intensity of 1H, confirming the deprotonated structure of the nitrile-enolato ligands.…”

“…This value is comparable to those reported for the N-bound cyanoenolato (2110-2200 cm -1 ) [39][40][41][42] or keteniminato complexes (2120-2190 cm -1 ). [43][44][45][46][47] Two absorptions observed at 1405-1422 and 1509-1592 cm -1 are assignable to the enolate group. The molecular structure of 4h‚1.5C 2 H 4 Cl 2 established by X-ray diffraction study is given in Figure 1, and selected bond distances and angles are shown in Table 2.…”

A Lewis Acid Stabilized Ketenimine in an Unusual Variant of the Electrophilic Aromatic Substitution

“…[13] Especially in the 1960s and early 1970s, the chemistry of [C(CN) 3 ] À salts has been expanded to include many new classes of compounds such as covalent tricyanomethanides of the main groups, organometallic tricyanomethanides, or d-metal complexes with donor atoms of the 14 th to 16 th groups of the periodic table. [14,15] In 2017, Banert et al finally published a crystal structure data set for isolated HC(CN) 3 proving unequivocally the existence of tricyanomethane 1 a rather than its tautomeric form, dicyanoketenimine 1 b (Scheme 1). This X-ray study revealed strong hydrogen bonds that exist in the crystalline solid between the hydrogen atom and three nitrogen atoms of various neighbouring molecules, making 1 a significantly more stable as a crystalline pure substance than in solution.…”

“…Especially in the 1960s and early 1970s, the chemistry of [C(CN) 3 ] − salts has been expanded to include many new classes of compounds such as covalent tricyanomethanides of the main groups, organometallic tricyanomethanides, or d‐metal complexes with donor atoms of the 14 th to 16 th groups of the periodic table [14,15] . In 2017, Banert et al.…”

“…Especially in the 1960s and early 1970s, the chemistry of [C(CN) 3 ] − salts has been expanded to include many new classes of compounds such as covalent tricyanomethanides of the main groups, organometallic tricyanomethanides, or d‐metal complexes with donor atoms of the 14 th to 16 th groups of the periodic table. [ 14 , 15 ] In 2017, Banert et al. finally published a crystal structure data set for isolated HC(CN) 3 proving unequivocally the existence of tricyanomethane 1 a rather than its tautomeric form, dicyanoketenimine 1 b (Scheme 1 ).…”