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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Direct Transformation of SiH 4 to a Molecular L(H) 2 Co=Si=Co(H) 2 L Silicide Complex

The synthesis of bimetallic molecular silicide complexes is reported, based on the use of multiple Si–H bond activations in SiH 4 at the metal centers of 14-electron LCo I fragments (L = Tp", HB(3,5-diisopropylpyrazolyl) 3 – ; [BP 2 tBu Pz], PhB(CH 2 P t Bu 2 ) 2 (pyrazolyl)). Upon exposure of (Tp"Co) 2 (μ-N 2 ) (1) to SiH 4 , a mixture of (Tp"Co) 2 (μ-H) (2) and (Tp"Co) 2 (μ-H) 2 (3) was formed and no evidence for Si–H oxidative addition products was observed. In contrast, [BP 2 tBu Pz]-supported Co complexes led to Si–H oxidative additions with the generation of silylene and silicide complexes as products. Notably, the reaction of ([BP 2 tBu Pz]Co) 2 (μ-N 2 ) (5) with SiH 4 gave the dicobalt silicide complex [BP 2 tBu Pz](H) 2 Co=Si=Co(H) 2 [BP 2 tBu Pz] (8) in high yield, representing the first direct route to a symmetrical bimetallic silicide. Here, the effect of the [BP 2 tBu Pz] ligand on Co–Si bonding in 7 and 8 was explored by analysis of solid-state molecular structures and density functional theory (DFT) investigations. Upon exposure to CO or DMAP (DMAP = 4-dimethylaminopyridine), 8 converted to the corresponding [BP 2 tBu Pz]Co(L) x adducts (L = CO, x = 2; L = DMAP, x = 1) with concomitant loss of SiH 4 , despite the lack of significant Si–H interactions in the starting complex. On heating to 60 °C, 8 underwent reaction with MeCl to produce small quantities of Me x SiH 4–x (x = 1–3), demonstrating functionalization of the μ-silicon atom in a molecular silicide to form organosilanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Measurement of the decay rate of the SiH feature as a function of temperature

We have previously suggested that the SiH fundamental stretch could serve as a diagnostic indicator of the oxidation state of silicate surfaces exposed to the solar wind for prolonged periods. We have now measured the primary decay rate of SiH in vacuo as a function of temperature and find that the primary rate constant for the decay can be characterized by the following equation: k(min(exp -1)) approximately equals 0.186 exp(-9/RT) min(exp -1), where R = 2 x 10(exp -3) kcal deg(exp -1) mole(exp -1). This means that the half-life for the decay of the SiH feature at room temperature is approximately 20 yrs, whereas the half-life at a peak lunar regolith temperature of approximately 500K would be only approximately 20 days. At the somewhat lower temperature of approximately 400K the half-life for the decay is on the order of 200 days. The rate of loss of SiH as a function of temperature provides an upper limit to the quantity of H implanted by the solar wind which can be retained by a silicate grain in a planetary regolith. This will be discussed in more detail here.

Nuth, Joseph A., III↗
NASA NTRS1988

SiH and the unidentified 4.6 micron feature

Results from experimental studies of the irradiation of SiH4-H2O and Fe(CO)5-SiH4-H2O ice mixtures at 15 K using 1 MeV protons have revealed the synthesis of a very stable infrared spectral feature at 4.6 microns which is characteristic of the SiH functional group. This feature persists through warmup of the ice, exposure to air at 300 K, and vacuum annealing to at least 400 K. Because of the high cosmic abundance of both silicon and hydrogen and the unexpected stability of the SiH feature in our experiments, it is suggested that SiH might be responsible for the 4.6 micron absorption feature observed in W33A.

Nuth, Joseph A.↗
NASA NTRS1991

The SiH vibrational stretch as an indicator of the chemical state of interstellar grains

The infrared spectra of amorphous silicate grains and films formed in a variety of laboratory experiments have been measured. It is found that the frequency of the SiH fundamental stretch is extremely sensitive to the chemical environment of the grain in which the silicon is bound and varies from 2270/cm in oxidized grains to 2110/cm in a reducing environment. It is proposed that features previously observed in W33A could be due to -SiH groups in amorphous silica, partially reduced silica, silicon nitride or slightly oxidized silicon carbide. It is predicted that observations at 2270/cm will reveal a feature due to -SiH groups in highly oxidized interstelar and circumstellar grains. Such a feature might also appear in the spectra of comets.

Moore, Marla H.↗
NASA NTRS1992

The -SiH vibrational stretch as an indicator of the oxidation state of silicon in a cometary or asteroidal regolith

It has been experimentally shown that the position of the -SiH fundamental vibrational stretch is very sensitive to the chemical environment surrounding the Si atom. Si in an oxidizing environment will display an -SiH feature near 4.4 microns, whereas Si in a reducing grain could be responsible for a feature at 4.74 microns. It is further shown that, as an oxidized grain is reduced, the -SiH fundamental shifts to longer wavelengths through a series of intermediate bands.

Nuth, Joseph A., III↗
NASA NTRS1972

RKR Franck-Condon factors for blue and ultraviolet transitions of some molecules of astrophysical interest and some comments on the interstellar abundance of CH, CH+ and SiH+.

RKR Franck-Condon factors for thirteen of the blue and ultraviolet transitions of AlF, AlO, BH, BD, CH, CD, CH(+), SiO and SiH(+) have been calculated. The interstellar abundances of CH, CH(+) and SiH(+) are discussed with regard to recent laboratory measurements, our Franck-Condon factors, and observations of the sun and the interstellar medium.

Liszt, H. S.↗
NASA NTRS1984

The far-infrared laser magnetic resonance spectrum of the SiH radical and determination of ground state parameters

The far-infrared laser magnetic resonance spectrum of the SiH radical in the v = O level of its X2Pi state has been recorded. The signals are rather weak. The molecules were generated in the reaction between fluorine atoms and SiH4. Rotational transitions have been detected in both 2Pi1/2 and 2Pi3/2 spin components but no fine structure transitions between the spin components were observed. Proton hyperfine splittings were resolved on some lines. The measurements have been analyzed, subjected to a least-squares fit using an effective Hamiltonian, and the appropriate molecular parameters determined. The weakness of the spectrum and the failure of attempts to power saturate favorable lines are both consistent with a small value for the electric dipole moment for SiH.

Brown, J. M.↗
NASA NTRS1985

The microwave and far-infrared spectra of the SiH radical

Consideration of Si's cosmic abundance leads to the expectation that the related molecule SiH may be detected in extraterrestrial sources. A tabulation is presented of frequencies, wavelengths, and line strengths for SiH molecule transitions at microwave and far-IR wavelengths, on the basis of an analysis of its laser magnetic resonance spectrum. It is hoped that the frequencies presented will be useful to both laboratory spectroscopists and astrophysicists.

Brown, J. M.↗
DOE OSTI2020

Materials Data on SiH by Materials Project

SiH is Cubane-like structured and crystallizes in the trigonal P-3m1 space group. The structure is zero-dimensional and consists of two silylidyne molecules. Si is bonded in a single-bond geometry to one H atom. The Si–H bond length is 1.50 Å. H is bonded in a single-bond geometry to one Si atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Nd2Fe15(SiH)2 by Materials Project

Nd2Fe15(SiH)2 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. Nd is bonded in a distorted bent 120 degrees geometry to eight Fe, one Si, and two equivalent H atoms. There are a spread of Nd–Fe bond distances ranging from 3.05–3.35 Å. The Nd–Si bond length is 3.09 Å. Both Nd–H bond lengths are 2.46 Å. There are six inequivalent Fe sites. In the first Fe site, Fe is bonded to two equivalent Nd, eight Fe, and two equivalent Si atoms to form distorted FeNd2Fe8Si2 cuboctahedra that share corners with eight FeNd2Fe8Si2 cuboctahedra, corners with four equivalent HNd2Fe4 octahedra, edges with three FeNd2Fe8Si2 cuboctahedra, edges with two equivalent HNd2Fe4 octahedra, and faces with nine FeNd2Fe8Si2 cuboctahedra. The corner-sharing octahedra tilt angles range from 24–29°. There are a spread of Fe–Fe bond distances ranging from 2.40–2.70 Å. Both Fe–Si bond lengths are 2.74 Å. In the second Fe site, Fe is bonded in a single-bond geometry to four Fe, two equivalent Si, and one H atom. There are two shorter (2.44 Å) and one longer (2.52 Å) Fe–Fe bond lengths. There are one shorter (2.70 Å) and one longer (2.71 Å) Fe–Si bond lengths. The Fe–H bond length is 1.86 Å. In the third Fe site, Fe is bonded to two equivalent Nd, eight Fe, and two equivalent Si atoms to form distorted FeNd2Fe8Si2 cuboctahedra that share corners with fourteen FeNd2Fe8Si2 cuboctahedra, edges with two equivalent FeNd3Fe8Si cuboctahedra, faces with ten FeNd2Fe8Si2 cuboctahedra, and faces with four equivalent HNd2Fe4 octahedra. All Fe–Fe bond lengths are 2.43 Å. Both Fe–Si bond lengths are 2.58 Å. In the fourth Fe site, Fe is bonded to two equivalent Nd, eight Fe, and two equivalent Si atoms to form distorted FeNd2Fe8Si2 cuboctahedra that share corners with eight FeNd2Fe8Si2 cuboctahedra, corners with two equivalent HNd2Fe4 octahedra, edges with four FeNd3Fe8Si cuboctahedra, faces with eight FeNd2Fe8Si2 cuboctahedra, and faces with two equivalent HNd2Fe4 octahedra. The corner-sharing octahedral tilt angles are 47°. All Fe–Fe bond lengths are 2.43 Å. Both Fe–Si bond lengths are 2.58 Å. In the fifth Fe site, Fe is bonded to three equivalent Nd, eight Fe, and one Si atom to form FeNd3Fe8Si cuboctahedra that share corners with eleven FeNd2Fe8Si2 cuboctahedra, corners with four equivalent HNd2Fe4 octahedra, edges with four FeNd2Fe8Si2 cuboctahedra, faces with eight FeNd2Fe8Si2 cuboctahedra, and faces with two equivalent HNd2Fe4 octahedra. The corner-sharing octahedra tilt angles range from 63–71°. Both Fe–Fe bond lengths are 2.50 Å. The Fe–Si bond length is 2.58 Å. In the sixth Fe site, Fe is bonded in a single-bond geometry to four Fe, one Si, and one H atom. The Fe–Si bond length is 2.58 Å. The Fe–H bond length is 1.98 Å. Si is bonded in a 7-coordinate geometry to one Nd, twelve Fe, and one Si atom. The Si–Si bond length is 2.55 Å. H is bonded to two equivalent Nd and four Fe atoms to form HNd2Fe4 octahedra that share corners with ten FeNd2Fe8Si2 cuboctahedra, corners with two equivalent HNd2Fe4 octahedra, edges with two equivalent FeNd2Fe8Si2 cuboctahedra, and faces with six FeNd2Fe8Si2 cuboctahedra. The corner-sharing octahedral tilt angles are 61°.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Ancillary Steric Effects on the Activation of SiH Bonds in Arylsilazido Rare-Earth Compounds

Three new hydridosilazido ligands, –N(SiHMe 2 )Aryl (Aryl = Ph, 2,6-C 6 Me 2 H 3 (dmp), 2,6-C 6 iPr 2 H 3 (dipp)) and their rare-earth complexes Ln{N(SiHMe 2 )Aryl} 3 (THF) n (Ln = Sc, Y, Lu; Aryl = Ph, n = 2; Aryl = dmp, n = 1; Aryl = dipp, n = 0) were synthesized to study the relationships among ligand steric properties, secondary Ln←H–Si bonding, and the reactivity of amide and SiH groups. In these compounds, the steric encumbrance of the aryl group was systematically increased from phenyl to 2,6-dimethylphenyl to 2,6-diisopropylphenyl. NMR, IR, and X-ray diffraction studies of the complexes characterize the number of secondary interactions and additional THF ligands coordinated to the rare-earth centers. The complexes with the smallest phenylsilazido ligands, Ln{N(SiHMe 2 )Ph} 3 (THF) 2 , contain features associated with three nonbridging 2-center-2-electron (2c-2e) Si–H bonds. Characterization of intermediate-sized Ln{N(SiHMe 2 )dmp} 3 THF reveals three and two Ln←H–Si interactions for yttrium and lutetium analogues, respectively, with both metals having one coordinated THF per complex. Ln{N(SiHMe 2 )dipp} 3 is formed solvent-free, and all three ligands adopt Ln←H–Si bonding modes. The reaction between Ln{N(SiHMe 2 )dipp} 3 and ketones provides the hydrosilylated product via addition of C=O and Si–H bonds, which occurs rapidly even at low temperature. Furthermore, this reaction is proposed to occur through an associative mechanism on the basis of negative activation entropy measured for substitution of pyridine in Ln{N(SiHMe 2 )dipp} 3 ·NC 5 H 5 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Si–Cl Bond Activations at Ni(0) to Give Bimetallic Ni(I) μ 1,2 -Cl–SiR 1 R 2 Complexes that Undergo Selective Hydrogenolyses to R 1 R 2 SiH 2 Dihydrosilanes

Chlorosilanes are cheap and abundant raw materials as crucial building blocks in silicon chemistry, yet the metal-mediated activation and functionalization of Si–Cl bonds typically require precious metal sources due to their thermodynamic inertness. Herein, we report the stoichiometric, facile activation, and hydrogenolysis of chlorosilanes mediated by a series of low-valent NHC–Ni (NHC = N-heterocyclic carbene) complexes. Treatment of a Ni(0) complex (IPr)Ni(η 6 -toluene) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene) with chlorosilanes (R 1 R 2 SiCl 2 , R 1 = Cl, R 2 = Cl, Me, Ph, or R 1 = R 2 = Me, Et, Ph, 4-MePh) rapidly afforded di-Ni(I) complexes with a bridging silyl ligand ([(IPr)Ni] 2 (μ-SiR 1 R 2 Cl)(μ-Cl), 1 R1,R2 ) in high yields. Use of a bulkier chlorosilane, Ph 2 SiCl 2 , allowed the isolation of the mono-Ni(II) silyl complex (IPr)Ni(SiPh 2 Cl)Cl (2 Ph ) as an intermediate generated via Si–Cl oxidative addition, which underwent comproportionation with (IPr)Ni(η 6 -toluene) to form 1 Ph,Ph in nearly quantitative yield. Interestingly, 1 R1,R2 was found to react with H 2 at room temperature to form mono- or di-hydrosilanes in moderate to high yields, and the product selectivity was found to be highly dependent on the identity of substituents on Si. In conclusion, these results demonstrate a novel example of facile Si–Cl activation and hydrogenolysis mediated by low-valent mono- and dinuclear NHC–Ni complexes under mild conditions.

Liu, Tianchang [University of California, Berkeley↗
NASA NTRS1985

Ignition of mixtures of SiH sub 4, CH sub 4, O sub 2, and Ar or N sub 2 behind reflected shock waves

Ignition delay times in mixtures of methane, silane, and oxygen diluted with argon and nitrogen were measured behind reflected shock waves generated in the chemical kinetic shock tube at Langley Research Center. The delay times were inferred from the rapid increase in pressure that occurs at ignition, and the ignition of methane was verified from the emission of infrared radiation from carbon dioxide. Pressures of 1.25 atm and temperatures from 1100 K to 1300 K were generated behind the reflected shocks; these levels are representative of those occurring within a supersonic Ramjet combustor. Expressions for the ignition delay time as a function of temperature were obtained from least squares curve fits to the data for overall equivalence ratios of 0.7 and 1.0. The ignition delay times with argon as the diluent were longer than those with nitrogen as the diluent. The infrared wavelength observations at 4.38 microns for carbon dioxide indicated that silane and methane ignited simultaneously (i.e., within the time resolution of the measurement). A combined chemical kinetic mechanism for mixtures of silane, methane, oxygen, and argon or nitrogen was assembled from one mechanism that accurately predicted the ignition of methane and a second mechanism that accurately predicted silane hydrogen ignition. Comparisons between this combined mechanism and experiment indicated that additional reactions, possibly between silyl and methyl fragments, are needed to develop a good silane methane mechanism.

Mclain, A. G.↗
NASA NTRS1986

Theoretical electric dipole moments of SiH, GeH and SnH

Accurate theoretical dipole moments have been computed for the X2Pi ground states of Si(-)H(+) (0.118 D), Ge(+)H(-) (0.085 D), and Sn(+)H(-) (0.357 D). The trend down the periodic table is regular and follows that expected from the electronegativities of the group IV atoms. The dipole moment of 1.24 + or - 0.1 D for GeH recently derived by Brown, Evenson and Sears (1985) from the relative intensities of electric and magnetic dipole transitions in the 10-micron spectrum of the X2Pi state is seriously questioned.

Pettersson, L. G. M.↗
NASA NTRS1986

Theoretical Electric Dipole Moments of SiH, GeH and SnH

Accurate theoretical dipole moments (mu(sub c) have been computed for the X(exp 2)Pi ground states of Si(-)H(+)(0.118 D), Ge(+)H(-)(0.085 D) and Sn(+)H(-)(0.357 D). The trend down the periodic table is regular and follows that expected from the electronegativities of the group IV atoms. The dipole moment of 1.24 +/- 0.1 D for GeH recently derived by Brown, Evenson and Sears from the relative intensities of electric and magnetic dipole transitions in the 10 microns spectrum of the X(exp 2)Pi state is seriously questioned.

Pettersson, Lars G. M.↗