Germane photochemistry. Photolysis of gas mixtures of planetary interest

Guillemin, Jean‐Claude; Lassalle, L.; Janati, Tajdine

doi:10.1016/0032-0633(94)00164-m

Cited by 18 publications

(11 citation statements)

References 25 publications

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“…[18][19][20]23,24 Not much is known about the chemistry of these species because they have been synthesized for the first time only a few years ago and because some of them are not very stable. 25,26 The experimental determination of their intrinsic acidities and a theoretical estimate of their intrinsic basicities were reported recently in the literature 18,23 and show significant dissimilarities between C-and Si-or Ge-containing compounds. Later on we have also shown 19,20 that the reactivity of these compounds toward Cu + presents important peculiarities.…”

Section: Introductionmentioning

confidence: 94%

The importance of agostic-type interactions for the binding energies of Ni⁺to saturated and α,β-unsaturated alkanes, silanes and germanes

Corral¹,

Mó²,

Yáñez³

2003

New J. Chem.

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The gas-phase interaction of H 3 C-CH 2 -XH 3 and H 2 C=C(H)XH 3 (X ¼ C, Si, Ge) with Ni + has been investigated through the use of high-level density functional theory methods. The structures of the corresponding Ni + complexes were optimized at the B3LYP/6-311G(d,p) level of theory. Final energies were obtained in single-point B3LYP/6-311+G(2df,2p) calculations. In all cases, the most stable complexes are stabilized through agostic-type interactions between the metal cation and the hydrogen atoms of the XH 3 group. Only for propene is the conventional p-complex the global minimum of the potential energy surface. These agostic-type linkages can be viewed as three-center bonds resulting from electron-donor interactions between s bonding orbitals of the neutral and the empty s orbital of the metal and back-donation from pairs of valence electrons of the metal into the corresponding s* antibonding orbitals of the neutral. As a consequence, these bonds are particularly stable for Si-and Ge-containing compounds, because of the high electron-donor ability of the XH 3 group when the heteroatom is Si or Ge. Vinylsilane and vinylgermane lead to non-conventional complexes in which the metal bridges the C a atom of the C=C double bond and one of the hydrogen atoms of the XH 3 group. In contrast with the behavior predicted when the reference acid is Cu + , Si-and Ge-derivatives, both saturated and unsaturated, bind Ni + more strongly than propane and propene, respectively. Ni + binding energies are systematically greater than Cu + binding energies and the bond activation effects observed upon Ni + attachment are sizably larger than those found upon Cu + association. Computational detailsThe B3LYP density functional theory approach, combined with a 6-311+G(2df,2p) basis set, has been proved to be very

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Section: Introductionmentioning

confidence: 94%

The importance of agostic-type interactions for the binding energies of Ni⁺to saturated and α,β-unsaturated alkanes, silanes and germanes

Corral¹,

Mó²,

Yáñez³

2003

New J. Chem.

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“…During the last four years, we have reported the alkenylation, allenylation, or alkynylation of GeCl 4 , SnCl 4 , AsCl 3 , or SbCl 3 by vinylic, allenyl, and alkynyltri- n -butylstannane. We have recently described the formation of allylic dihalophosphines, -arsines, and -stibines by reaction of an allylic tri- n -butylstannane with PCl 3 or PBr 3 , AsCl 3 , or SbCl 3 respectively …”

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confidence: 99%

Synthesis and Characterization of Allylic Dihaloboranes

and

Guillemin

1997

Organometallics

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Volatile allylic dihaloboranes have been prepared and characterized by 1H, 11B, 13C, and 19F NMR spectroscopy and mass spectrometry. The stability (τ1/2) of such compounds in dilute CDCl3 solutions depends on the substituents and the halides and ranges from a few minutes (allylic dibromoboranes) to several days (allylic difluoroboranes). Allyldihaloborane etherates were obtained by addition of diethyl ether to the corresponding free allyldihaloborane.

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“…Strobel, 1977;Ferris et al, 1984). It has also been suggested as a destruction mechanism for GeH 4 (Guillemin et al, 1995) and could plausibly apply to AsH 3 too. Geometry effects mean that higher latitudes receive fewer UV photons from the sun, and the higher opacity of stratospheric aerosols in the polar regions also acts as a shield to UV light (Zhang et al, 2013).…”

Section: Latitudinal Profilesmentioning

confidence: 94%

Latitudinal variability in Jupiter's tropospheric disequilibrium species: GeH$_4$, AsH$_3$ and PH$_3$

Giles,

Fletcher,

Irwin

2016

Preprint

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Jupiter's tropospheric composition is studied using high resolution spatially-resolved 5-μm observation from the CRIRES instrument at the Very Large Telescope. The high resolving power (R=96,000) allows us to spectrally resolve the line shapes of individual molecular species in Jupiter's troposphere and, by aligning the slit north-south along Jupiter's central meridian, we are able to search for any latitudinal variability. Despite the high spectral resolution, we find that there are significant degeneracies between the cloud structure and aerosol scattering properties that complicate the retrievals of tropospheric gaseous abundances and limit conclusions on any belt-zone variability. However, we do find evidence for variability between the equatorial regions of the planet and the polar regions. Arsine (AsH 3 ) and phosphine (PH 3 ) both show an enhancement at high latitudes, while the abundance of germane (GeH 4 ) remains approximately constant. These observations contrast with the theoretical predictions from Wang et al. (2016) and we discuss the possible explanations for this difference.

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Germane photochemistry. Photolysis of gas mixtures of planetary interest

Cited by 18 publications

References 25 publications

The importance of agostic-type interactions for the binding energies of Ni⁺to saturated and α,β-unsaturated alkanes, silanes and germanes

The importance of agostic-type interactions for the binding energies of Ni⁺to saturated and α,β-unsaturated alkanes, silanes and germanes

Synthesis and Characterization of Allylic Dihaloboranes

Latitudinal variability in Jupiter's tropospheric disequilibrium species: GeH$_4$, AsH$_3$ and PH$_3$

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Germane photochemistry. Photolysis of gas mixtures of planetary interest

Cited by 18 publications

References 25 publications

The importance of agostic-type interactions for the binding energies of Ni+to saturated and α,β-unsaturated alkanes, silanes and germanes

The importance of agostic-type interactions for the binding energies of Ni+to saturated and α,β-unsaturated alkanes, silanes and germanes

Synthesis and Characterization of Allylic Dihaloboranes

Latitudinal variability in Jupiter's tropospheric disequilibrium species: GeH$_4$, AsH$_3$ and PH$_3$

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Product

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The importance of agostic-type interactions for the binding energies of Ni⁺to saturated and α,β-unsaturated alkanes, silanes and germanes

The importance of agostic-type interactions for the binding energies of Ni⁺to saturated and α,β-unsaturated alkanes, silanes and germanes