Reactions of germanium(II), tin(II), and antimony(III) chlorides with acenaphthene-1,2-diimines

Abstract

Reactions of diimines dtb BIAN and dph BIAN with GeCl 2 afford germanium(II) com plexes with radical anionic ligands, (dtb BIAN)GeCl (5) and (dph BIAN)GeCl (6a), re spectively, where dtb BIAN is 1,2 bis[(2,5 di tert butylphenyl)imino]acenaphthene and dph BIAN is 1,2 bis[(2 biphenyl)imino]acenaphthene. The latter reaction gives 6a along with [(dph BIAN)GeCl] + [GeCl 3 ] -(6b). The reactions of tin(II) and antimony(III) chlorides with dtb BIAN and dpp BIAN produce complexes of these halides with neutral coordinated diimines, viz., (dtb BIAN)SnCl 2 (7) and (dpp BIAN)SbCl 3 (8) (dpp BIAN is 1,2 bis[(2,6 di isopropyl phenyl)imino]acenaphthene). Paramagnetic complexes 5 and 6a were studied by ESR spec troscopy. Diamagnetic compounds 7 and 8 were characterized by 1 H NMR spectroscopy. The structures of complexes 5, 6a,b, 7, 8, and (dpp BIAN)Ge (9) were established by X ray diffraction analysis.

Alkylmagnesium Complexes with the Rigid dpp‐bian Ligand {dpp‐bian = 1,2‐Bis[(2,6‐diisopropylphenyl)imino]acenaphthene}

“…The Mg–O( t Bu) bond lengths in 5 [1.963(3) and 1.953(3) Å] are fairly similar as the Mg–O distances in dimeric magnesium ketiminate [{CH[C(Me)NC 6 H 4 ‐2‐OMe] 2 }MgO t Bu] 2 [1.944(2) and 1.965(2) Å] 6. As in other metal complexes of the dpp‐bian radical anion,4 the C(1)–N(1) and C(2)–N(2) bond lengths in 2 – 5 [1.324(6)–1.343(3) Å] are longer than in free dpp‐bian [both 1.282(4) Å]7 and in metal complexes containing neutral dpp‐bian ligands, for example, (dpp‐bian)SnCl 4 [1.291(8) and 1.286(8) Å]8 and (dpp‐bian)SnCl 2 [1.283(1) and 1.269(1) Å] 9…”

N-Heterocyclic Germylenes NHGe – Old Trends and New Developments

“…Further evidence for the cationic NHGe's demand for electron density can be seen in the reaction [NHGeCl{W(CO) 5 }] with NaBPh 4 . In the course of the reaction, the cationic NHGe-W(CO) 5 complex reacts with its NaBPh 4 anion, usually regarded as inert, under abstraction of phenyl anion and generation of BPh 3 (Fig.…”

Synthesis and characterization of metal complexes supported by bis (arylimino) acenaphthene

“…in which the ligand formed a radical anion. 51 The EPR spectrum for both 1.25 and 1.26 revealed coupling between the unpaired electron and the Ge, Cl and N nuclei. However the 73 Ge, 35 Cl, and 37 (1.26), 51 as determined by SCXRD.…”

“…With the aim of synthesizing tin analogs of the germylenes, metathesis reaction of SnCl2 with the disodium salt of Dipp-BIAN ligand [(dipp-BIAN)Na2] was studied. 51 47 In contrast to the Mes-BIAN ligand, the reaction of SnCl2 with dtb-BIAN ligand did not lead to disproportionation of the metal center but gave the corresponding Sn(II) complex [(dtb-BIAN)SnCl2] (1.29) instead. 51 (Scheme 1.13) X-ray crystallographic analysis on 1.29 revealed that the SnCl2 is coordinated to only one N atom from the dtb-BIAN ligand.…”

“…51 47 In contrast to the Mes-BIAN ligand, the reaction of SnCl2 with dtb-BIAN ligand did not lead to disproportionation of the metal center but gave the corresponding Sn(II) complex [(dtb-BIAN)SnCl2] (1.29) instead. 51 (Scheme 1.13) X-ray crystallographic analysis on 1.29 revealed that the SnCl2 is coordinated to only one N atom from the dtb-BIAN ligand. However, its 1 H NMR spectrum in C6D6 suggested the presence of a mirror plane bisecting the N-C-C-N framework since the tert-butyl groups on each diimine moiety appeared to be magnetically equivalent.…”