scholarly journals Stabilizing Magnesium Hydride Complexes with Neutral Ligands

2019 ◽  
Vol 2019 (41) ◽  
pp. 4433-4439 ◽  
Author(s):  
Michael Wiesinger ◽  
Brant Maitland ◽  
Holger Elsen ◽  
Jürgen Pahl ◽  
Sjoerd Harder
2019 ◽  
Vol 48 (46) ◽  
pp. 17174-17178 ◽  
Author(s):  
Lucas A. Freeman ◽  
Jacob E. Walley ◽  
Diane A. Dickie ◽  
Robert J. Gilliard

Herein we report the synthesis and characterization of dinuclear magnesium–hydride complexes coordinated by NHCs, [(IiPrMe2)Mg(μ-H)(N(SiMe3)2)]2and {(IiPrMe2)Mg(μ-H)[((CH2)Me2Si)2N]}2(IiPrMe2= N,N’-diisopropyl-2,3-dimethylimidazol-2-ylidine).


2003 ◽  
Vol 68 (10) ◽  
pp. 1877-1896 ◽  
Author(s):  
Karel Mach ◽  
Róbert Gyepes ◽  
Michal Horáček ◽  
Lidmila Petrusová ◽  
Jiří Kubišta

New tetramethylphenylcyclopentadienyl trinuclear titanocene hydride-magnesium hydride complexes [{Ti(η5-C5Me4R)2(μ-H)2}2Mg], where R = Ph (1) or 4-fluorophenyl (FPh; 2), the dinuclear [Ti(η5-C5Me4Ph)[η5:η1{Ti:Mg}-C5Me4(o-C6H4)](μ-H)2Mg(THF)2] (3) and [Ti(η5-C5Me4Ph)2(μ-H)2MgC(Me)=CHMe] (4) complexes, and the [{Ti(η5-C5Me4Ph)2(η1-C≡CSiMe3)2}-{MgCl(THF)}+] (5) tweezer complex initiated the dimerization of (trimethylsilyl)ethyne (TMSE) or 1-hexyne (HXYN) to exclusively head-to-tail (HTT) dimers at 60 °C with the turnover number ranging from 300 to 500 mol alkyne per mol of the Ti complex. In contrast, all of them were inactive in the dimerization of tert-butylethyne (TBUE). Monitoring of reactions of the 1-5 complexes with the alkynes by electron spin resonance (ESR) method revealed a decay of the initial complexes 1-5 in the dimerizing systems with TMSE and HXYN or a conversion of complexes 3, 4, and 5 into the Ti(III) acetylide [Ti(η5-C5Me4Ph)2(η1-C≡CCMe3)] (6) in systems with TBUE. The acetylide 6 also initiated the dimerization of TMSE and HXYN to HTT dimers only. This fact together with the absence of ESR signals of tweezer complexes and acetylides in the reacting hydride systems allow us to assume that the rate of conversion of complexes 1-4 to tweezer complexes is slower than the rate of dissociation of the tweezer complexes to give the acetylides which are apparently the ultimate catalytic species. Most of the evidence on the catalytic complexes has been obtained from ESR spectra which are reliably characteristic of each type of the complexes. Crystal structures of 4 and 6 were determined.


The system of bands in the visible region of the emission spectrum of magnesium hydride is now well known. The bands with heads at λλ 5622, 5211, 4845 were first measured by Prof. A. Fowler, who arranged many of the strongest lines in empirical series for identification with absorption lines in the spectra of sun-spots. Later, Heurlinger rearranged these series in the now familiar form of P, Q and R branches, and considered them, with the OH group, as typical of doublet systems in his classification of the fine structure of bands. More recently, W. W. Watson and P. Rudnick have remeasured these bands, using the second order of a 21-foot concave grating, and have carried out a further investigation of the fine structure in the light of the present theory of band spectra. Their detection of an isotope effect of the right order of magnitude, considered with the general structure of the system, and the experimental work on the production of the spectrum, seems conclusive in assigning these bands to the diatomic molecule MgH. The ultra-violet spectrum of magnesium hydride is not so well known. The band at λ 2430 and the series of double lines in the region λ 2940 to λ 3100, which were recorded by Prof. Fowler in 1909 as accompanying the group of bands in the visible region, appear to have undergone no further investigation. In view of the important part played by hydride band spectra in the correlation of molecular and atomic electronic energy levels, it was thought that a study of these features might prove of interest in yielding further information on the energy states of the MgH molecule. The present paper deals with observations on the band at λ 2430; details of an investigation of the other features of the ultra-violet spectrum will be given in a later communication.


Author(s):  
Ming Huang ◽  
Yinwu Li ◽  
Xiao-Bing Lan ◽  
Jiahao Liu ◽  
Cunyuan Zhao ◽  
...  

Metal hydride complexes are key intermediates for N-alkylation of amines with alcohols by borrowing hydrogen/hydrogen autotransfer (BH/HA) strategy. Reactivity tuning of metal hydride complexes could adjust the dehydrogenation of alcohols...


Author(s):  
Jan Pecak ◽  
Sarah Fleissner ◽  
Luis F. Veiros ◽  
Ernst Pittenauer ◽  
Berthold Stöger ◽  
...  

2021 ◽  
Author(s):  
Yihang Li ◽  
Jia Sheng Ng ◽  
Bin Wang ◽  
Shunsuke Chiba
Keyword(s):  

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