688-73-3Relevant articles and documents
Baum,Considine
, p. 1267 (1964)
Metal hydrides as electron donors. The mechanism of oxidative cleavage with tris(phenanthroline) complexes of iron(III)
Wong,Klingler,Kochi
, p. 423 - 430 (1980)
The group 4 metal hydrides HMR3 (M = silicon, germanium, tin; R = alkyl, phenyl) react spontaneously with 2 equiv of tris(phenanthroline)iron(III) perchlorate, FeL3(ClO4)3, in acetonitrile solutions. Although the second-order kinetics (first order in each reactant) indicate that the selective cleavage of only the hydrido-metal bond proceeds from a rate-limiting bimolecular process, there is no significant deuterium kinetic isotope effect. The free-energy dependence of the second-order rate constant kH for the silicon and germanium hydrides follows the Marcus relationship with slope α close to the theoretical value of 8.5 for an outer-sphere electron-transfer process. The paramagnetic cation HMR3+, similar to that formed by electron impact or photoionization of HMR3, is postulated to be a metastable intermediate which undergoes spontaneous scission of the hydrogen-metal bond, followed by a further rapid oxidation of the fragment by a second equivalent of FeL33+. The rate-limiting, outer-sphere mechanism for HMR3 accords with that previously established for electron transfer between the related series of peralkylmetals MR4 and the same FeL33+ complexes. The electron-transfer rate constants kH and kR for HMR3 and MR4, respectively, are compared for their sensitivity to changes in the standard reduction potentials E° of FeL33+ and the gas-phase ionization potentials ID of HMR3 and MR4. Polarization and solvation effects appear to be especially important in electron transfer from metal hydrides, especially those of tin.
Tamborski et al.
, p. 237 (1963)
Aluminumoxyhydride: Improved synthesis and application as a selective reducing agent
Tewari, Brij B.,Shekar, Sukesh,Huang, Longchuan,Gorrell, Carolyn E.,Murphy, Timothy P.,Warren, Kevin,Nesnas, Nasri,Wehmschulte, Rudolf J.
, p. 8807 - 8811 (2006)
Aluminumoxyhydride (HAlO) has been obtained by the reaction of aluminum hydride with the siloxane (Me2HSi)2O or the stannoxane (Bu3Sn)2O as an amorphous colorless insoluble powder. The highest-purity product resulted from the reaction of H3Al· NMe3 with (Me2HSi)2O. However, HAlO suspensions in tetrahydrofuran (THF) of sufficient quality for synthetic applications can be prepared from commercially available reagents with only minor precautions. A LiAlH4 solution in THF was treated successively with Me 3SiCl and (Me2HSi)2O, followed by heating at 60°C for 20 h. The resulting suspensions are 0.4-0.5 M in active hydride content and selectively reduce aldehydes and ketones to the respective alcohols in the presence of any other common nonprotic functional group.
METHOD FOR PRODUCING 14 GROUP METAL LITHIUM COMPOUND
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Paragraph 0044; 0066, (2016/10/31)
PROBLEM TO BE SOLVED: To provide a method for quantitatively producing a group 14 metal lithium compound under a mild condition. SOLUTION: The method for producing a group 14 metal lithium compound represented by formula (4): R4-nMLin comprises reacting a compound represented by formula (1): R4-nMXn and lithium in the presence of a polycyclic aromatic compound represented by formula (2) or formula (3). [In formula (1) and formula (2), R is a hydrocarbon group; M is a metal atom selected from Si, Ge and Sn; X is a halogen atom or R3M- (R and M are the same as mentioned above); and n is 1 or 2] and [R1 is H or a hydrocarbon group; and m is an integer of 0 to 5.] SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
A convenient route to distannanes, oligostannanes, and polystannanes
Khan, Aman,Gossage, Robert A.,Foucher, Daniel A.
, p. 1046 - 1052 (2011/02/16)
The quantitative conversion of the tertiary stannane (ν;-Bu) 3SnH (2) into (ν-Bu)6Sn2 (4) was achieved by heating the neat hydride material under low pressure or under closed inert atmosphere conditions. A 31% conversion of Ph3SnH (3)to Ph6Sn 2 (5) was also observed under low pressure; however, under closed inert atmosphere conditions afforded Ph4Sn (6) as the major product. A mixed distannane, (ν-Bu)3SnSnPh3 (7), can also be prepared in good yield utilizing an equal molar ratio of 2 and 3 and the same reaction conditions used to prepare 4. This solvent-free, catalyst-free route to distannanes was extended to a secondary stannane, (ν-Bu)2SnH 2 (8), which yielded evidence (NMR) for hydride terminated distannane H(ν-Bu)2SnSn(ν-Bu)2H(9), the polystannane [(ν-Bu)2Sn] ' (10), and various cyclic stannanes [(ν- Bu)2Sn]ν=5,6=5,6 (11, 12). Further evidence for 10 was afforded by gel permeation chromatography (GPC) where a broad, moderate molecular weight, but highly dispersed polymer, was obtained (Mw = 1.8 × 104 Da, polydispersity index (PDI) = 6.9) and a characteristic UV-vis absorbance (1max)of ν370 nm observed.