144435-57-4Relevant academic research and scientific papers
Mechanistic studies of the addition of carbonyl compounds to tetramesityldisilene and tetramesitylgermasilene
Samuel, Mini S.,Jenkins, Hilary A.,Hughes, Donald W.,Baines, Kim M.
, p. 1603 - 1611 (2003)
The mechanism for the addition of carbonyl compounds to disilenes and germasilenes was investigated by examination of the structure of the products obtained from the reaction of the modified mechanistic probe, trans,trans-2-methoxy-3-phenylcyclopropane carbaldehyde, with tetramesityldisilene and tetramesitylgermasilene. The aldehyde was found to undergo characteristic ring-opening reactions depending on whether a radical or a cation develops at the carbinyl carbon. Thus, reaction of the mechanistic probe under ionic conditions (p-TsOH) yielded a mixture of cis- and trans-2-methoxy-3-phenyl-2,3-dihydrofuran (6) from ring-opening toward the methoxy substituent. In contrast, reaction of the mechanistic probe under radical conditions (HSi(SiMe3)3, AIBN) yielded a mixture of cis- and trans-3-methoxy-4-phenyl-1-[tris(trimethylsilyl)siloxy]but-1-ene (7) from regioselective ring-opening toward the phenyl substituent. 2,2,3,3-Tetramesityl-4-phenyl-5-methoxyoxa-2,3-disilacyclohept-6-ene (8) was formed from the reaction between the aldehyde and tetramesityldisilene, and a mixture of three isomers of 2,2,3,3-tetramesityl(phenyl)(methoxy)oxagermasilacyclohept-6-ene (10a-c) and [dimesityl(1-oxa-4-methoxy-5-phenylpentadienyl)silyl]germane (10d) was formed in the reaction of the aldehyde with tetramesitylgermasilene. The formation of 8, 10a, 10b, and 10d provides unequivocal evidence for the presence of radical intermediates in the addition of carbonyl compounds to the disilene and germasilene.
Mechanistic Studies of the Addition of Carbonyl Compounds to Tetramesityldigermene
Samuel, Mini S.,Baines, Kim M.
, p. 12702 - 12703 (2003)
The mechanism of the addition of carbonyl compounds to digermenes was investigated by examining the reaction between tetramesityldigermene and two mechanistic probes: trans-2-phenylcyclopropane carbaldehyde and trans,trans-2-methoxy-3-phenylcyclopropane c
Addition of chloroform to tetramesityldigermene
Samuel, Mini S.,Jennings, Michael C.,Baines, Kim M.
, p. 590 - 592 (2008/10/08)
The addition of chloroform to tetramesityldigermene yields 1,1,2,2-tetramesityl-1-chloro-2-(dichloromethyl)digermane in 25% isolated yield.
The addition of oxygen to tetramesityldigermene
Samuel, Mini S.,Jennings, Michael C.,Baines, Kim M.
, p. 130 - 137 (2007/10/03)
The addition of atmospheric oxygen to tetramesityldigermene under a variety of conditions was studied. The addition of oxygen to the digermene, prepared by the photolysis of hexamesitylcyclotrigermane in THF, cleanly afforded 3,3,4,4-tetramesityl-3,4-digermadioxetane (7). The photolysis of hexamesitylcyclotrigermane in toluene in the presence of triethylsilane under the ambient atmosphere gave a very complex product mixture, from which 2,2,4,4-tetramesityl-2,4-digermadioxetane (9), tetramesityldigermaoxirane (10) and 2,2,4,4,5,5-hexamesityl-2,4,5-trigermadioxolane (11) were isolated and identified. The structures of compounds 9 and 11 were determined by X-ray crystallography.
The reaction of group 14 dimetallenes with alkenes: Electron-poor alkenes
Dixon, Craig E.,Cooke, Jeffrey A.,Baines, Kim M.
, p. 5437 - 5440 (2008/10/08)
The addition reactions of tetramesitylgermasilene with methyl vinyl ketone (MVK), crotonaldehyde, and acrylonitrile were studied. When tetramesitylgermasilene was allowed to react with MVK, [2 + 4] cycloaddition and nonregioselective carbonyl [2 + 2] cycloaddition products were isolated. When tetramesitylgermasilene was allowed to react with crotonaldehyde, the carbonyl [2 + 2] adduct was produced exclusively. The regiochemistry was not determined. The addition of acrylonitrile to tetramesitylgermasilene yielded a germasilacyclobutane, which is the formal [2 + 2] cycloadduct between the germasilene and the C-C double bond of acrylonitrile. Tetramesityldisilene was also found to yield a formal [2 + 2] adduct with acrylonitrile. However, tetramesityldigermene rearranges to a germylgermylene at a faster rate than acrylonitrile addition.
Reaction of group 14 dimetallenes with alkenes: Electron-rich alkenes
Dixon, Craig E.,Liu, Hui W.,Vander Kant, Christopher M.,Baines, Kim M.
, p. 5701 - 5705 (2008/10/09)
The addition reactions of tetramesitylgermasilene with 1-methoxybutadiene, ethyl vinyl ether, vinyl acetate, or styrene were studied. When tetramesitylgermasilene was allowed to react with 1-methoxybutadiene or styrene, formal [2+2] addition products were isolated. The addition of styrene to tetramesitylgermasilene was determined to be completely regioselective. In the presence of ethyl vinyl ether or vinyl acetate, tetramesitylgermasilene undergoes a 1,2-mesityl shift yielding a silylgermylene, at a faster rate than addition to either alkene. Tetramesityldisilene was also found to yield a formal [2+2] adduct with styrene. However, tetramesityldigermene rearranges to a germylgermylene at a faster rate than styrene addition.
Thermolysis of hexamesitylsiladigermirane or hexamesitylcyclotrigermane in the presence of 2,3-dimethylbutadiene or water
Baines, Kim M.,Cooke, Jeffrey A.,Dixon, Craig E.,Liu, Hui Wen,Netherton, Matthew R.
, p. 631 - 634 (2008/10/08)
The thermolysis of hexamesitylsiladigermirane and hexamesitylcyclotrigermane in the presence of 2,3-dimethylbutadiene (DMB) or water has been investigated. Thermolysis of hexamesitylsiladigermirane (1) in the presence of DMB results in the formation of two major compounds: 1,1-dimesityl-3,4-dimethyl-1-germacyclopent-3-ene (3) and 1-mesityl-1-(trimesitylsilyl)-3,4-dimethyl-1-germacyclopent-3-ene (4). Compounds 3 and 4 are most probably formed by initial thermal regioselective cleavage of the siladigermirane to give tetramesitylgermasilene and dimesitylgermylene, which is immediately trapped by the diene. The germasilene does not appear to react with DMB but rather, under the reaction conditions, undergoes a 1,2-mesityl shift at a faster rate to give a silylgermylene, which is subsequently trapped by the diene. Similarly, thermolysis of hexamesitylcyclotrigermane (5) in the presence of DMB yields compounds 3 and 1-mesityl-1-(trimesitylgermyl)-3,4-dimethyl-1-germacyclopent-3-ene (6), in contrast to an earlier report. Again, the intermediate digermene rearranges to a germylgermylene, which is the species trapped, at a faster rate than reaction with DMB. Thermolysis of 1 or 5, in the presence of water, results in the formation of products clearly derived from the addition of water across the double bond of the intermediate germasilene or digermene. Unlike the addition of methanol, the addition of water across the germasilene is not completely regioselective. The synthetic utility and mechanistic implications of this reaction are discussed.
Tetramesitylgermasilene: The first relatively stable germasilene and its rearrangement to a silylgermylene
Baines, Kim M.,Cooke, Jeffrey A.
, p. 3487 - 3488 (2008/10/08)
The thermolysis of hexamesitylsiladigermirane (1) in the presence of triethylsilane at 105°C yields mesityl(triethylsilyl)(trimesitylsilyl)germane (3) and dimesityl(triethylsilyl)germane (4). Photolysis of 1 at -78°C in the presence of triethylsilane gave tetramesitylgermasilene, which upon warming rearranged by a 1,2-aryl shift to mesityl(trimesitylsilyl)germylene, which was then trapped by the silane.
A Facile Digermene-to-germylgermylene Rearrangement; Bulky Germylene Insertion into the Si-H Bond
Baines, Kim M.,Cooke, Jeffrey A.,Vittal, Jagadese J.
, p. 1484 - 1485 (2007/10/02)
The thermolysis of hexamesitylcyclotrigermane 1 in the presence of triethylsilane at 105 deg C yields dimesityl(triethylsilyl)germane 2 and 1,1,1,2-tetramesityl(2-triethylsilyl)digermane 3; the molecular structure of 3 has been determined by X-ray crystallography.
