The title compound Dipp(H)P–P(H)Dipp where Dipp = 2,6-diisopropylyphenyl has been prepared starting from DippPH2 via DippPHLi reacting 2:1 with BrCH2CH2Br. A high-resolution single-crystal X-ray diffraction study at 153 ± 2 K provides an accurate description of the structure in the solid state, only the fourth dihydro diorganophosphane to have been so characterized. The Raman spectrum of the solid shows an intense, broad peak for P–H stretching at 2314 cm−1 and two peaks at 460 and 450 cm−1 for P–P stretching, assignments confirmed by RHF/6-31G+(3d,2p) frequency calculations undertaken on the anti conformers. 31P, 31P{1H }, 1H{31P}, and 13C{1H } solution NMR spectra in CDCl3 are consistent with the presence of 58% meso and 42% rac diastereomers. Analysis of their AA′XX′ spin systems enabled calculation of 1JPP′ values of (–)189 and (–)205 Hz, respectively. A B3LYP/6-31G(d,p) computational analysis of the energetics of rotation about the P–P bond in both diastereomers shows that the anti and two gauche conformers are likely to be populated approximately equally in each. The resulting average ϕ angles (torsions of the phosphorus lone pairs) are 110° for meso and 103° for rac; the smaller ϕ angle fits with the larger 1JPP′ value for the rac isomer.
The preparation of the bulky secondary amide N-(2,6-diisopropylphenyl)-2,2-dimethylpropanamide and the determination of its crystal structure at 173(2) K are reported. The structure displays disorder of the tBu methyl groups due to thermal motion and an infinite N–H····O=C hydrogen-bonded chain described by a [Formula: see text] graph set. Reaction of this amide with ZnCl2 or ZnBr2 in tetrahydrofuran (THF) results in dihalo-(tetrahydrofurano)-(N-(2,6-diisopropylphenyl)–2,2-dimethylpropanamido)-zinc(II) complexes (Cl, Br) for which the crystal structures have also been determined. These complexes, as well as a chloroform solvate of the dichloro-complex, contain N–H····X–Zn hydrogen-bonded chains described by [Formula: see text] graph sets. Evaporative crystallization results in the loss of both chloroform and THF to afford crystals determined to be bis(μ2-chloro)-dichloro-bis(N-(2,6-diisopropylphenyl)-2,2-dimethylpropanamido)-dizinc(II) by single crystal X-ray diffraction. This dimeric complex shows a complex network of N–H····Cl–Zn hydrogen bonds describable by [Formula: see text], [Formula: see text], and [Formula: see text] chains, small [Formula: see text] molecular “squares”, and larger [Formula: see text] rings.
In the title compound, C16H26NO+·Cl−·0.5H2O, the asymmetric unit consists of two independent cations, their respective chloride anions and a solvent water molecule. Together they form a discrete crescent-shaped entity linked by hydrogen bonds from the central water atom to two Cl− ions and from the latter to two protonated imine groups. The geometries of the two independent cations are essentially the same. The planar N=C(O)CH3 groups in each (r.m.s. deviations = 0.0011 and 0.0026 Å) form dihedral angles of 75.28 (5) and 79.10 (4)° with the benzene rings. In one cation, the methyl atoms of one of the isopropyl groups were modeled as disordered over two sets of sites, with refined occupancies of 0.589 (17) and 0.411 (17).
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