Binuclear Zinc Complexes with Radical-Anionic Diimine Ligands

Abstract

The reactions of (dpp-BIAN)Zn−Zn(dpp-BIAN) (1) with PhCCH and of [(dpp-BIAN)Zn(μ-I)]2 (2) with potassium hydride yield the binuclear complexes [(dpp-BIAN)Zn(μ-CCPh)]2 (3) and [(dpp-BIAN)Zn(μ-H)]2 (4), respectively (dpp-BIAN = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene). Complex 3 is also obtained by thermal dehydrogenation of [dpp-BIAN(H)]Zn(CCPh) (5), which in turn can be prepared by reacting ZnI2 with equimolar amounts of [dpp-BIAN(H)]Na and PhCCNa. The paramagnetic compounds 3 and 4 have been characterized by ESR spectroscopy; the diamagnetic complex 5, by 1H NMR spectroscopy. The molecular structures of 3 and 4 have been determined by single-crystal X-ray diffraction. The electronic structure of complex 4 has been examined by DFT.

Mononuclear Phenolate Diamine Zinc Hydride Complexes and Their Reactions With CO2

“…1a,18 These complexes exhibit a range of structures, including clusters, 15 cubanes, 6,11,13 dimers, 1c,12a,14,17,19 and mononuclear structures. 2b,9b,12d,16,18 The carbon dioxide insertion chemistry of only a few of these hydride complexes has been studied.…”

Novel Synthetic Pathway for New ZnZn‐Bonded Compounds from Dizincocene

“…[9] Herein, we report on the reaction of dizincocene with the potassium salt of tris(3,5-dimethylpyrazolyl)hydridoborate, The solid-state structures of 1 (Figure 1) and 2 ( Figure 2) were determined by single-crystal X-ray diffraction.…”

“…with CÀH acidic phenylacetylene occurred with H 2 elimination and formation of a binuclear, acetylene-bridged Zn II complex (redox reaction) rather than with protonation of the Dipp-BIAN substituent. [9] Herein, we report on the reaction of dizincocene with the potassium salt of tris ( Compound 1 was obtained in an almost quantitative yield (> 90 %) by the reaction of [Zn 2 Cp* 2 ] with KA C H T U N G T R E N N U N G (Tp Me 2 ) (2 equiv) in THF at À30 8C. The yield of 90 % is significantly higher than yields reported for Zn I complexes obtained from reduction reactions.…”

Zinc–zinc bonded decamethyldizincocene Zn2(η5-C5Me5)2 as catalyst for the inter- and intramolecular hydroamination reaction

“…We used the addition of 2,4,6-trimethylaniline to phenylethyne as a standard reaction because this reaction has also been studied with many other reported catalysts (Table 1). 17 Although a titanium catalyst is shown in [8][9][10][11]. With typical catalyst and cocatalyst loading of 2.5 mol% each the isolated yield was 99% for this catalytic reaction (Table 2, entry 1E).…”