Daniella Schuchmann

Structural Characterization of a Base-Stabilized [Zn2]2+ Cation

The landmark discovery of decamethyldizincocene [Cp*2Zn2] (1; Cp* = C5Me5) by Carmona et al. in 2004 [1] has led to increasing research on the synthesis of low-valent metal complexes of Group 2 and 12 metals in recent years and several complexes containing Mg Mg, Cd Cd, 4] Hg Hg and Zn Zn bonds, which are typically kinetically stabilized by use of sterically demanding or chelating organic substituents, have been synthesized. However, it should be noted that the first molecular complex with a Zn Zn bond, Zn2H2, was trapped in an argon matrix at 12 K and characterized by vibrational spectroscopy and computational calculations. With respect to the rather large number of organometallic complexes containing a direct Zn Zn bond it is somehow surprising how little is know about the [Zn2] 2+

The Reaction of Dizincocene with Preservation of the ZnZn Bond

Since the epoch-making synthesis of [Cp*2 Zn2] (1; Cp* = Me5C5), [1] the first complex containing a Zn Zn bond, by Carmona et al. in 2004, four compounds of the type R2Zn2 have been synthesized and structurally characterized that are stabilized by sterically demanding organic substituents: R = EtMe4C5, [2] [2,6-(2,6-iPr2C6H3)2C6H3], [3] [{(2,6iPr2C6H3)NC(Me)}2CH], [4] [(2,6-iPr2C6H3)NC(Me)]2, [5]

Reactions of dizincocene with sterically demanding bis(iminodi(phenyl) phosphorano) methanes

Reactions of Cp*(2)Zn(2) with sterically demanding bis(iminodi(phenyl)phosphorano)methanes LH (LH = CH(2)(Ph(2)P=NR)(2) (R = Ph L(1)H, SiMe(3)L(2)H, 2,6-i-Pr(2)C(6)H(3) (Dipp) L(3)H) at ambient temperature occurred with elimination of Cp*H and subsequent formation of the homoleptic complex L(1)(2)Zn(2)1 and the heteroleptic complexes LZnZnCp* (L = L(2)2, L(3)3, L(1)4). 3 is the first structurally characterized heteroleptic organozinc complex with the zinc atoms in the formal oxidation state +1.

Solid-state and Solution Studies on a β-Diketiminate Zinc Hydride Complex

[MesnacnacZn(μ-H)]2 (1) was synthesized by reaction of MesnacnacZnI with either an equimolar amount of KNH(iPr)BH3 or an excess of NaH and characterized by multinuclear NMR and IR spectroscopy as well as X-ray diffraction. Two polymorphs of 1 were found and their structures determined on single crystals Graphical Abstract Solid-state and Solution Studies on a β-Diketiminate Zinc Hydride Complex

Low-temperature thermolysis behavior of tetramethyl- and tetraethyldistibines.

The thermolysis behavior of tetramethyl- and tetraethyldistibine (Sb2Me4 and Sb2Et4) was investigated using a mass spectrometer coupled to a tubular flow reactor under near-chemical vapor deposition (CVD) conditions. Sb2Me4 undergoes a gas-phase disproportionation with an estimated activation energy of 163 kJ/mol. This reaction leads to the formation of methylstibinidine, SbMe, that reacts on the surface to produce antimony film and SbMe3. Unfortunately, this clean decomposition pathway is limited to a narrow temperature range of 300–350°C. At temperatures exceeding 400°C, SbMe3 decomposes following a radical route with a consequent risk of carbon contamination. In contrast, Sb2Et4 disproportionates at the hot wall of the reactor. According to mass-spectrometric data, this reaction is significant starting at a temperature of 100°C, with an apparent activation energy of 104 kJ/mol. Within the temperature range of 100–250°C, the precursor decomposition leads to the formation of antimony films and SbEt3, whereas different molecular reaction pathways are significantly activated above 250°C. The use of Sb2Et4 lowers the risk of carbon contamination compared to Sb2Me4 at high temperature. Therefore, Sb2Et4 is a promising CVD precursor for the growth of antimony films in the absence of hydrogen atmosphere in a wide temperature range.