The gas-phase reaction of SiH2 with dimethylether: kinetic evidence for direct formation of a donor–acceptor adduct

Investigation of the Prototype Silylene Reaction, SiH2 + H2O (and D2O): Time-Resolved Gas-Phase Kinetic Studies, Isotope Effects, RRKM Calculations, and Quantum Chemical Calculations of the Reaction Energy Surface

“…The pressure dependences for SiH 2 + D 2 O were very similar and are not shown. The pressure and temperature effects are consistent with those of a third body assisted association process although not as extensive as those obtained in other such reaction systems of silylene. − ,,,, The RRKM calculations are described in the next section.

3 Pressure dependence of the second-order rate constants for SiH 2 + H 2 O at 296 K (▪) and 339 K (▿).

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The reaction between silylene and ammonia: Some gas-phase kinetic and quantum chemical studies

“…The results of these experiments are shown in Figures 1 and 2. Reasonable linear fits were obtained, as expected for second order kinetics, although it should be noted that there is slightly higher scatter than is usually obtained in this kind of study [5][6][7][8][9][10][11][12][13][14][15][16][17][18]. Because the rate constants showed a dependence on laser pulse energy, two plots are shown, one for higher pulse energies (60 mJ) and one for lower values (ca 30 mJ).…”

“…SiH 2 also has a great affinity for electronegative elements and will react with lone pair donor species containing the elements of N, O, F, P, S and Cl amongst others [4]. We, and others, have recently studied the kinetics of its reactions with "O-donor" molecules, H 2 O [5,6], CH 3 OH (CD 3 OD) [5], Me 2 O [7,8], Me 2 CO [9], MeCHO [10,11], CO [12], CO 2 [13] and O 2 [14] itself, and also with "Cldonor" molecules, HCl [15] and CH 3 Cl [16]. We have also previously reported kinetic studies of the reactions of SiH 2 with the N-containing molecules N 2 O [17], NO [18] and even N 2 [19] (although no reaction was found in this case).…”

Molecular Main Group Metal Hydrides

“…We would like to draw specific attention to the review by Hadlington, Driess, and Jones who document the use of modern molecular design principles and synthetic methods to access low-coordinate Group 14 hydride complexes, while discussing important pioneering work relating to the use of such species in catalysis . The parent inorganic silylene SiH 2 is often touted as a key intermediate formed during the decomposition of SiH 4 into thin films of Si. , As shown in Scheme , SiH 2 can be generated as a transient species by the flash photolysis of PhSiH 3 , while photolysis of Me 2 SiH 2 and 1-chloro-1-silacyclopent-3-ene ( 738 ) yield MeSiH and ClSiH, respectively. , The reactivity of SiH 2 with small molecules, such as O 2 , H 2 O, HCl, CO 2 , MeC­(O)­H, Me 2 O, alkenes, , alkynes, N 2 (the H 2 Si·N 2 adduct is stable at 10 K), NO, or silanes (e.g., MeSiH 3 ), can lead to E–H bond insertion, oxidative addition, hydride migration, or Lewis acid–base adduct formation, depending on the nature of the substrate (Scheme ). Furthermore, SiH 2 also has been the subject of numerous computational investigations. − Laser flash photolysis of germacyclopentenes at 193 nm (Scheme ) yields GeH 2 , either in the gas phase or solution, , and reactivity paths that mirror those exhibited by SiH 2 with small molecules have been observed. − In related work, gas phase laser flash photolysis of 1,3,4-trimethyl­germacyclopent-3-ene ( 739 ) yields transient MeGeH (Scheme ), while passage of an electric discharge through H 3 GeCl vapor affords the reactive halogermylene HGeCl .…”

“…977,978 As shown in Scheme 119, SiH 2 can be generated as a transient species by the flash photolysis of PhSiH 3 , while photolysis of Me 2 SiH 2 and 1-chloro-1- silacyclopent-3-ene (738) yield MeSiH and ClSiH, respectively. 979,980 The reactivity of SiH 2 with small molecules, such as O 2 , 981 H 2 O, 982 HCl, 983 CO 2 , 984 MeC(O)H, 985 Me 2 O, 986 alkenes, 987,988 alkynes, 989 N 2 (the H 2 Si•N 2 adduct is stable at 10 K), 990 NO, 991 or silanes (e.g., MeSiH 3 ), 992 can lead to E−H bond insertion, oxidative addition, hydride migration, or Lewis acid−base adduct formation, depending on the nature of the substrate (Scheme 120). Furthermore, SiH 2 also has been the subject of numerous computational investigations.…”