156398-89-9Relevant academic research and scientific papers
Synthesis and molecular structures of α-diimines and their zinc and palladium dichloride complexes
Coventry, David N.,Batsanov, Andrei S.,Goeta, Andres E.,Howard, Judith A.K.,Marder, Todd B.
, p. 2789 - 2795 (2004)
Three α-iimines have been prepared and structurally characterised by single-crystal X-ray diffraction. In addition, molecular structures of some of their tetrahedral ZnCl2 and square-planar PdCl2 complexes are reported allowing a comparison as a function of coordination geometry. Three α-diimines, 2,3-dimethyl-N,N′-bis(cyclohexyl)-diaza-1,4-butadiene, Cy-DAD (1), (DAD = diaza-1,4-butadiene), bis{2,8-(4-methoxyphenylimino)} acenaphthene, p-OMe-BIAN (3), (BIAN = 2,8-bis(arylimino)acenaphthene) and bis{2,8-(2,6-di-isopropylphenylimino)}acenaphthene, 2,6-iPr-BIAN (4), were synthesised either via their zinc complexes, as a template, or by the direct reaction of the appropriate primary amine with the diketone. Compound 1 is a non-constrained analogue of the rigid, bidentate nitrogen ligands 3 and 4. Syntheses of the zinc and palladium complexes of 3 and 4, namely 2, 5, 6 and 7, are also reported herein. All compounds have been characterised spectroscopically, and the molecular structures of 1, 3, 4, ZnCl 2(p-OMe-BIAN)·1/2CH2Cl2 (2), PdCl 2(p-OMe-BIAN) (6) and PdCl2(2,6-iPr-BIAN) (7) have been determined by single-crystal X-ray diffraction. Compound 1 adopts a transoid geometry and possesses a crystallographic inversion centre midway along the N=C-C=N backbone. Compounds 3 and 4 are inherently cisoidal and X-ray analysis highlights a twofold axis through the backbone. The Pd(II) centres of 6 and 7 both adopt square planar geometries whilst 6 contains four molecules per asymmetric unit and 1/2 molecule of benzonitrile per Pd atom and complex 7 is isomorphous with the known structure of PdCl(Me)(2,6-iPr-BIAN). The Zn complex 2 is pseudo tetrahedral as expected for Zn(II).
Synthesis, characterization of zinc complexes with neutral α-diimine ligands and application in ring-opening polymerization of σ-caprolactone
Wang, Xiaodan,Liu, Xuehong,Huang, Ju
, p. 773 - 776 (2017/12/08)
A series of neutral α-diimine ligands with diacetyl and acenaphthenequinone skeletons were prepared by the reaction between diacetyl and the corresponding aromatic amine. These ligands reacted with ZnCl2 to generate symmetric α-diimine zinc complexes C1-C
Synthesis and Catalysis of Redox-Active Bis(imino)acenaphthene (BIAN) Iron Complexes
Villa, Matteo,Miesel, Dominique,Hildebrandt, Alexander,Ragaini, Fabio,Schaarschmidt, Dieter,Jacobi von Wangelin, Axel
, p. 3203 - 3209 (2017/08/29)
Reactions of various substituted bis(imino)acenaphthenes (R-BIANs) with FeCl2(thf)1.5 afforded the tetrahedral complexes (R-BIAN)FeCl2 (2) from bulky α-diimines and the octahedral complexes [Fe(R-BIAN)3][FeCl4]2 (3) from less bulky ligands. The driving force for the formation of complexes 3 is the high ligand-field stabilization of the low-spin FeII center. The two sets of complexes exhibit distinct charge-transfer band intensities and redox activities. (R-BIAN)FeCl2 complexes showed reversible ligand-centered reductions at ?0.9 V (vs. FcH/FcH+; FcH: ferrocene); further reduction led to decomposition. Irreversible oxidations were observed at 0.2 and 0.4 V, associated with a reduction at ?0.4 V, as well as a ligand-centered redox event at 1.0 V. First applications of the Fe(BIAN) complexes to hydrogenations of alkenes indicated good catalytic activity under mild conditions.
Synthesis and characterization of rigid bidentate nitrogen ligands and some examples of coordination to divalent palladium. X-ray crystal structures of bis(p-tolylimino)acenaphthene and methylchloropalladium(II)
Asselt, Rob van,Elsevier, Cornelis J.,Smeets, Wilberth J. J.,Spek, Anthony L.,Benedix, Roland
, p. 88 - 98 (2007/10/02)
The synthesis and characterization of the rigid bidentate nitrogen ligands bis-(phenylimino)camphane (Ph-BIC) and a series of bis(arylimino)acenaphthenes (Ar-BIAN) is described.These ligands were synthesized by the reaction of camphorquinone or acenaphthenequinone with the corresponding (substituted) aniline in the presence of ZnCl2 or NiBr2, followed by removal of the metal salt in a subsequent step.NDDO calculations on pTol-BIAN showed that the electronic properties of this ligand are comparable to the open-chain analogue Ph-DAB (DAB = 1,4-diaza-1,3-butadiene).The aromatic group on the imine N atom of Ar-BIAN ligands is oriented out of the bis(imino)acenaphthene plane, leading to the formation of syn and anti isomers for the ortho-substituted derivatives o-MeC6H4-BIAN and o-iPrC6H4-BIAN.In solution one isomer is observed for these ligands, but upon coordination to a Pd(Me)Cl fragment both syn and anti forms are present, as two isomers are formed.Furthermore, the attempted synthesis of bis(isopropylimino)cyclohexane is described, but it was found that a tautomeric imine-enamine compound is formed which coordinates to palladium(II) in a monodentate fashion, which could not be converted to a chelating ligand.The structure of pTol-BIAN and Pd(Me)Cl(o,o'-iPr2C6H3-BIAN) in the solid state were determined by X-ray diffraction. pTol-BIAN is monoclinic, space group C2, a = 20.021(2), b = 8.7703(10), c = 5.5664(10) Angstroem, β = 103.37(1) deg, Z = 2, final R = 0.040 for 963 reflections with I>2.5?(I).Pd(Me)Cl(o,o'-iPr2C6H3-BIAN) is orthorhombic, space group Pbca, a = 11.440(2), b = 21.250(3), c = 27.087(2) Angstroem, Z = 8, final R = 0.043 for 2433 reflections with I>2.0?(I).
