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Hydrosilylation and Hydrogermylation of CO2 and CS2 by Al and Ga Functionalized Silanes and Germanes – Cooperative Reactivity with Formation of Silyl Formates and Disilylacetals
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-08-25 , DOI: 10.1002/ejic.202000723 Michael Tolzmann 1 , Lina Schürmann 1 , Alexander Hepp 1 , Werner Uhl 1 , Marcus Layh 1
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-08-25 , DOI: 10.1002/ejic.202000723 Michael Tolzmann 1 , Lina Schürmann 1 , Alexander Hepp 1 , Werner Uhl 1 , Marcus Layh 1
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Hydrometallation of the alkynylelement hydrides iPr2E(H)–C≡C‐tBu (1; E = Si, Ge) with R2M–H [M = Al, Ga; R = tBu, CH(SiMe3)2] afforded in moderate yields the Al and Ga functionalized alkenylsilanes and ‐germanes iPr2E(H)C(MR2)=CH‐tBu (2). The air and moisture sensitive Al compounds reacted with CO2 under mild conditions (room temperature, 1 bar) to yield the formates [iPr2EC(AlR2)=C(H)–tBu]O2CH (3) by C=O insertion into the E–H bond and coordination of the second O atom to aluminum. The acetal MeAl[C(SiiPr2)=CH‐tBu]2O2CH2 (4a) was obtained as a unique side‐product. The less Lewis acidic Ga compound 2c did not react with CO2 even at higher temperature and pressure. Reaction with CS2 yielded the dithioacetals [iPr2EC(MtBu2)=CH‐tBuS]2CH2 (6) by reduction of both C=S bonds. Compounds 6 have two ECMS heterocycles bridged by a CH2 group. The reaction of the Ga compound 2c required elevated temperature (40 °C). At 70 °C the formal elimination of H2C=CMe2 and “CH4” afforded the unusual gallium sulfide {iPr2SiC[Ga(tBu)(µ‐S)]=CH‐tBu}2 (7c) which crystallized as a dimer with a central Ga2S2 heterocycle that is joined via its Ga–S edges to two four‐membered GaSCSi heterocycles.
中文翻译：
Al和Ga官能化的硅烷和锗烷的CO2和CS2的氢化硅烷化和氢化锗化–形成甲硅烷基和二甲硅烷基缩醛的协同反应性
所述alkynylelement氢化物的Hydrometallation我镨2 E（2H）-C≡C-吨卜（1 ; E =硅，锗），其中R 2 M-H [M =铝，镓; R =吨卜，CH（森达3）2 ]在中等产率的Al和Ga官能alkenylsilanes和得到-germanes我镨2 E（H）C（MR 2）= CH-吨BU（2）。空气和湿气敏感的Al化合物在温和的条件下（室温，1 bar）与CO 2反应生成甲酸酯[ i Pr 2 EC（AlR 2）= C（H）– t通过C = O插入E–H键和第二个O原子与铝的配位来生成Bu] O 2 CH（3）。乙缩醛MeAl [C（Si i Pr 2）= CH- t Bu] 2 O 2 CH 2（4a）作为独特的副产物获得。路易斯酸较少的酸性Ga化合物2c即使在较高的温度和压力下也不会与CO 2反应。与CS 2反应生成二硫缩醛[ i Pr 2 EC（M t Bu 2）= CH- t BuS] 2 CH 2（6）通过两个C ＝ S键的还原。化合物6具有两个通过CH 2基团桥接的ECMS杂环。Ga化合物2c的反应需要高温（40°C）。在70°C时，通过正式消除H 2 C = CMe 2和“ CH 4 ”，得到了异常的硫化镓{ i Pr 2 SiC [Ga（t Bu）（µ‐S）] = CH‐ t Bu} 2（7c）结晶为带有中心Ga 2 S 2杂环的二聚体，该中心通过其Ga-S边缘连接到两个四元GaSCSi杂环。
更新日期：2020-08-25
中文翻译：
Al和Ga官能化的硅烷和锗烷的CO2和CS2的氢化硅烷化和氢化锗化–形成甲硅烷基和二甲硅烷基缩醛的协同反应性
所述alkynylelement氢化物的Hydrometallation我镨2 E（2H）-C≡C-吨卜（1 ; E =硅，锗），其中R 2 M-H [M =铝，镓; R =吨卜，CH（森达3）2 ]在中等产率的Al和Ga官能alkenylsilanes和得到-germanes我镨2 E（H）C（MR 2）= CH-吨BU（2）。空气和湿气敏感的Al化合物在温和的条件下（室温，1 bar）与CO 2反应生成甲酸酯[ i Pr 2 EC（AlR 2）= C（H）– t通过C = O插入E–H键和第二个O原子与铝的配位来生成Bu] O 2 CH（3）。乙缩醛MeAl [C（Si i Pr 2）= CH- t Bu] 2 O 2 CH 2（4a）作为独特的副产物获得。路易斯酸较少的酸性Ga化合物2c即使在较高的温度和压力下也不会与CO 2反应。与CS 2反应生成二硫缩醛[ i Pr 2 EC（M t Bu 2）= CH- t BuS] 2 CH 2（6）通过两个C ＝ S键的还原。化合物6具有两个通过CH 2基团桥接的ECMS杂环。Ga化合物2c的反应需要高温（40°C）。在70°C时，通过正式消除H 2 C = CMe 2和“ CH 4 ”，得到了异常的硫化镓{ i Pr 2 SiC [Ga（t Bu）（µ‐S）] = CH‐ t Bu} 2（7c）结晶为带有中心Ga 2 S 2杂环的二聚体，该中心通过其Ga-S边缘连接到两个四元GaSCSi杂环。
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