N‐Heterocyclic Gallylene Supported Organoruthenium Derivatives – Synthesis, Structure, and C–H Bond Cleavage

Doddi, Adinarayana; Prabusankar, Ganesan; Gemel, Christian; Winter, Manuela; Fischer, Roland A.

doi:10.1002/ejic.201300257

Cited by 5 publications

(3 citation statements)

References 45 publications

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“…This allows for Al I to act as both a Z- and L-type ligand with respect to Rh. 43 Structurally related intermetallic compounds containing Pt 2 Ga 2 H 4 , 46 Ru 2 GaH 2 , 47 Ru 2 Ga 2 H 4 , 48 Ru 2 Al 2 H 4 , 48 Co 2 H 2 Al 2 , 49 Rh 2 Zn 2 H 2 groups are all known, 50 , 51 as are higher nuclearity species in which multiple main group fragments act as ligands for the transition metal (see ESI, † Fig. S1).…”

Section: Low-valent Main Group Ligands From Dehydrogenation (Tm←m)mentioning

confidence: 99%

Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals

Butler

Crimmin

2017

Chem. Commun.

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Section: Low-valent Main Group Ligands From Dehydrogenation (Tm←m)mentioning

confidence: 99%

Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals

Butler

Crimmin

2017

Chem. Commun.

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“…Even though the adaptation to a linear quadrupole analyzer has been accomplished, it never really succeeded as the kinetic energy spread of ions emerging from the emitter was not well suited for this type of mass analyzer. [144][145][146] The adaptation of FI, FD, and LIFDI to oaTOFs has been very successful and was commercialized by JEOL with the AccuTOF GC series [147][148][149][150][151][152][153][154][155] and by Waters with the GCT series of instruments. [156][157][158][159][160][161][162][163] As these oaTOF instruments, depending on the actual version of a particular instrument, provide a resolving power of 5000-10000, they are actually better suited for accurate mass measurements than scanning sector instruments.…”

Section: Mass Analyzers For Fi Fd and Lifdimentioning

confidence: 99%

From the discovery of field ionization to field desorption and liquid injection field desorption/ionization-mass spectrometry—A journey from principles and applications to a glimpse into the future

Gross

2020

Eur J Mass Spectrom (Chichester)

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The discovery of the ionizing effect of strong electric fields in the order of volts per Ångstrom in the early 1950s eventually led to the development of field ionization-mass spectrometry (FI-MS). Due to the very low ion currents, and thus, limited by the instrumentation of the 1960s, it took some time for the, by then, new technique to become adopted for analytical applications. In FI-MS, volatile or at least vaporizable samples mainly deliver molecular ions, and consequently, mass spectra showing no or at least minor numbers of fragment ion signals. The next major breakthrough was achieved by overcoming the need to evaporate the analyte prior to ionization. This was accomplished in the early 1970s by simply depositing the samples onto the field emitter and led to field desorption-mass spectrometry (FD-MS). With FD-MS, a desorption ionization method had become available that paved the road to the mass spectral analysis of larger molecules of low to high polarity and even of organic salts. In FD-MS, all of these analytes deliver spectra with no or at least few fragment ion peaks. The last milestone was the development of liquid injection field desorption/ionization (LIFDI) in the early 2000s that allows for sample deposition under the exclusion of atmospheric oxygen and water. In addition to sampling under inert conditions, LIFDI also enables more robust and quicker operation than classical FI-MS and FD-MS procedures. The development and applications of FI, FD, and LIFDI had mutual interference with the mass analyzers that were used in combination with these methods. Vice versa, the demand for using these techniques on other than magnetic sector instruments has effectuated their adaptation to different types of modern mass analyzers. The journey started with magnetic sector instruments, almost skipped quadrupole analyzers, encompassed Fourier transform ion cyclotron resonance (FT-ICR) and orthogonal acceleration time-of-flight (oaTOF) analyzers, and finally arrived at Orbitraps. Even interfaces for continuous-flow LIFDI have been realized. Even though being niche techniques to some degree, one may be confident that FI, FD, and LIFDI have a promising future ahead of them. This Account takes you on the journey from principles and applications of the title methods to a glimpse into the future.

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“…Gallylenes coordinated to transition metals represent more conventional organometallic Lewis pairs . Usually, stabilization of the gallium atom bearing a free electron pair is achieved by the use of some spacious ligand such as the cyclopentadienyl ligand, − β-diketiminate, − bulky silyl, aryl, , various pincer-type ligands, imino-amido ligands, − boryl, , or butadienyl . Indeed, the LGa ligand can be viewed isolobal/isoelectronic to CO and N 2 . − The structure, stability, and physical properties of LGa species , and their LAl − counterparts became much clearer after the exhausting studies within the last three decades.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of Transition Metal Gallylene Complexes Toward Substrates with Multiple Carbon–Element Bonds

et al. 2022

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Reactivity of transition metal complexes containing the redox-active gallylene (dpp-bian)Ga ligand (dpp-bian = 1,2-bis [(2,6-diisopropylphenyl)imino]acenaphthene) toward isocyanide, isocyanate, isothiocyanate, and ketene substrates is described. The reaction of [(dpp-bian)GaCr(CO) 5 ] (1) with tBuNC results in a dative complex [(dpp-bian)Ga(CNtBu)Cr(CO) 5 ] (2), while compound [(dppbian)GaCr(CO) 5 ] 2 [Na(THF) 2 ] 2 (3) reacts with tBuNC to give the coordination polymer [(dpp-bian)GaCr(CO) 5 ][Na(CNtBu)(THF)] n (5). Treatment of [(dppbian)GaCr(CO) 5 ] 2 [Na(THF) 2 ] 2 with an excess of PhNCO results in trimerization of the latter and formation of complex [(dpp-bian)GaCr(CO) 5 ][Na-(PhNCO) 3 (Et 2 O) (DME)] (4). [(dpp-bian)GaFeCp(CO) 2 ] (7) treated with Ph 2 CCO or PhNCS results in cycloaddition products [(dpp-bian)(Ph 2 CCO)-GaFeCp(CO) 2 ] ( 8) and [(dpp-bian)(PhNCS)GaFeCp(CO) 2 ] (9). The formation of 2 and 9 was found to be reversible, which offers a means for facile regulation of transition metal center reactivity and cooperative substrate activation. New compounds were characterized by EPR (2), NMR (4, 8, and 9), and IR spectroscopy (2, 4, 5, 8, and 9). The molecular structures of 2, 4, 5, 8, and 9 were established by single-crystal X-ray diffraction analysis. Electronic structures of the compounds have been examined by DFT calculations.

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N‐Heterocyclic Gallylene Supported Organoruthenium Derivatives – Synthesis, Structure, and C–H Bond Cleavage

Cited by 5 publications

References 45 publications

Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals

Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals

From the discovery of field ionization to field desorption and liquid injection field desorption/ionization-mass spectrometry—A journey from principles and applications to a glimpse into the future

Reactivity of Transition Metal Gallylene Complexes Toward Substrates with Multiple Carbon–Element Bonds

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