Electronic, Steric, and Ligand Influence on the Solid‐State Structures of Substituted Sodium and Potassium Anilides

Silylamide Complexes of Chromium(II), Manganese(II), and Cobalt(II) Bearing the Ligands N(SiHMe2)2 and N(SiPhMe2)2

“…Similar structures have been reported for calcium(II) 43 and ytterbium-(II), 44 but in contrast to compound 2, the latter display a center of symmetry (C 2 axis). Moreover, the angle between the N1− Cr1−N2 plane and the N3−Cr1−N4 plane is much smaller in the case of complex 2, with 35.86(7)°compared to 53.66°and 54.5(4)°for the calcium(II) and ytterbium(II) compounds, respectively.…”

“…As expected, the M1− N(SiMe 3 ) 2 and M1−NMe 2 distances are somewhat longer for the previously described complexes (Yb(II): 2.34(1) and 2.61(1) Å; Ca: 2.315(1) and 2.592(2) Å). 43,44 The core of {Co[N(SiMe 3 ) 2 ] 2 } 2 (μ-tmeda) (3, Figure 4) has an almost linear zigzag pattern propagating from N2 via the bridging tmeda to N3. The coordination geometry of the cobalt centers is distorted trigonal planar, and the M1−N bond lengths are shorter than in complex 2.…”

Synthesis and Crystal Structures of Lithium, Sodium, and ­Potassium Derivatives of 2‐(Methylthio)aniline and 2‐(Phenylthio)aniline

“…Generally, the dissimilarities of the metal nitrogen bond lengths in amide dimers (RN) 2 M 2 are described by the sp 2 hybridization of the amide nitrogen atom, which leads to a shorter contact to the sp 2 (2) ii 99. longer contact to the p electron pair. [16,18] In agreement with this assumption compound 6·DME displays two short K-N bonds (269.5(2), 272.5(2) pm), which are located in the H-N-C(ipso) plane of the amide nitrogen atoms N1 (Σ(angles): 357°) and N2 (Σ(angles): 358°). The remaining K-N bonds (281.3(2), 288.1(2) pm) are approx.…”

“…Comparable distances have been observed for [K(NPh 2 )(diox) 1.5 ] (K-N: 279.0-290.2 pm), [23] [K(NPh 2 )(THF) 3 ] (K-N: 279.5(2)-285.6(2) pm), [24] and [K(NPhiPr)(DME) 2 ] (284.8(2)-289.8(2) pm). [18] It is worthy to note that the dissimilarities of the K-N distances in compounds 5 and 6·DME are much more pronounced than in the reference compounds. Generally, the dissimilarities of the metal nitrogen bond lengths in amide dimers (RN) 2 M 2 are described by the sp 2 hybridization of the amide nitrogen atom, which leads to a shorter contact to the sp 2 (2) ii 99. longer contact to the p electron pair.…”

“…(235.9(2)-255.1(2) pm), [18] [{Na(NH-C 6 H 4 -2-OPh)(pmdta)} 2 ] (Na-N: 241.9(3)-242.8(3) pm), [19] [{Na(NHPh)(DME)} ϱ ] (Na-N: 240.7(1)-241.0(2) pm). [10] In analogy to the lithium derivatives 1·Et 2 O and 2·2THF the central Na 2 N 2 rings in compounds 3·DME and 4·DME are planar (1 symmetry) with obtuse N-Na-N angles (3·DME: 91.7(1)°, 4·DME: 97.9(1)°) and correspondingly acute Na-N-Na angles (3·DME: 88.3(1)°, 4·DME 82.1(1)°).…”