Abstract Transamination reactions of two different aminosilanes (trimethyl( tert -butylamino)silane and dimethyl(diamino)silane) with amines (diethylamine, pyrrolidine, tert -butylamine, iso -propylamine, and n -propylamine) are studied. For trimethyl(organoamino)silanes, the reaction of trimethyl( iso -propylamino)- or trimethyl(diethylamino)silane as aminosilanes and aniline or pyrrolidine are good starting materials to produce trimethyl(anilino)- and trimethyl(pyrrolidino)silane. The investigated equilibrium constants of the reactions of monoaminosilanes show a good correlation with quantum chemically calculated values. The reaction of two different diaminosilanes Me 2 Si(NR 1 R 2 ) 2 and Me 2 Si(NR 3 R 4 ) 2 containing different amino moieties leads to the formation of mixed diaminosilanes Me 2 Si(NR 1 R 2 )(NR 3 R 4 ) in most cases.
{"title":"Thermodynamics of transamination reactions with aminotrimethylsilanes and diaminodimethylsilanes","authors":"Steven Knerr, Marcus Herbig, Edwin Kroke","doi":"10.1515/mgmc-2022-8044","DOIUrl":"https://doi.org/10.1515/mgmc-2022-8044","url":null,"abstract":"Abstract Transamination reactions of two different aminosilanes (trimethyl( tert -butylamino)silane and dimethyl(diamino)silane) with amines (diethylamine, pyrrolidine, tert -butylamine, iso -propylamine, and n -propylamine) are studied. For trimethyl(organoamino)silanes, the reaction of trimethyl( iso -propylamino)- or trimethyl(diethylamino)silane as aminosilanes and aniline or pyrrolidine are good starting materials to produce trimethyl(anilino)- and trimethyl(pyrrolidino)silane. The investigated equilibrium constants of the reactions of monoaminosilanes show a good correlation with quantum chemically calculated values. The reaction of two different diaminosilanes Me 2 Si(NR 1 R 2 ) 2 and Me 2 Si(NR 3 R 4 ) 2 containing different amino moieties leads to the formation of mixed diaminosilanes Me 2 Si(NR 1 R 2 )(NR 3 R 4 ) in most cases.","PeriodicalId":18146,"journal":{"name":"Main Group Metal Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135611693","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tidiane Diop,Mouhamadou Birame Diop,Cheikh Abdoul Khadir Diop,Aminata Diasse-Sarr,Mamadou Sidibe,Florina Dumitru,Arie van der Lee
Abstract Three types of ladder-like organostannoxanes, [C5H4N(p-CO2)]2[Bu2Sn]4(μ 3-O)2(μ 2-OH)2 (1), [Ph2CHCO2]4[Bu2Sn]4(μ 3-O)2 (2), and [(p-NH2)-C6H4-CO2]2[Bu2Sn]4(μ 3 -O)2(μ 2 -OH)2 (3), have been synthesized and characterized using elemental analyses, Fourier-transform infrared spectroscopy, nuclear magnetic resonance (1H, 13C) experiments, and, for 1 and 2, single-crystal X-ray diffraction analysis. X-Ray diffraction discloses that complexes adopt tetranuclear tin(iv) ladder-like structures containing two (1) or four (2) deprotonated ligands. The essential difference between their molecular structures is that in 2 there are four carboxylate ligands, while in 1 and 3 there are two. The crystal structure of 1 reveals them to be a tetranuclear structure containing a three-rung-staircase Sn4O4 core. The Sn4O4 cluster consists of a ladder of four Sn2O2 units. For 2, the structure is a tetranuclear centrosymmetric dimer of an oxoditin unit having a central four-member ring. In this complex, the central Sn2O2 core is fused with two four-member and two six-member rings. In the structures, there are two types of tin ions arranged in distorted trigonal bipyramid geometry or octahedron geometry. A series of O–H⋯N, C–H⋯O, and C–H⋯π intermolecular hydrogen bonds in these complexes play an important function in the supramolecular, or two-dimensional network structures are formed by these interactions.
{"title":"Synthesis and structural characterization of new ladder-like organostannoxanes derived from carboxylic acid derivatives: [C5H4N(p-CO2)]2[Bu2Sn]4(μ 3 -O)2(μ 2 -OH)2, [Ph2CHCO2]4[Bu2Sn]4(μ 3 -O)2, and [(p-NH2)-C6H4-CO2]2[Bu2Sn]4(μ 3 -O)2(μ 2 -OH)2","authors":"Tidiane Diop,Mouhamadou Birame Diop,Cheikh Abdoul Khadir Diop,Aminata Diasse-Sarr,Mamadou Sidibe,Florina Dumitru,Arie van der Lee","doi":"10.1515/mgmc-2022-0008","DOIUrl":"https://doi.org/10.1515/mgmc-2022-0008","url":null,"abstract":"Abstract Three types of ladder-like organostannoxanes, [C5H4N(p-CO2)]2[Bu2Sn]4(μ 3-O)2(μ 2-OH)2 (1), [Ph2CHCO2]4[Bu2Sn]4(μ 3-O)2 (2), and [(p-NH2)-C6H4-CO2]2[Bu2Sn]4(μ 3 -O)2(μ 2 -OH)2 (3), have been synthesized and characterized using elemental analyses, Fourier-transform infrared spectroscopy, nuclear magnetic resonance (1H, 13C) experiments, and, for 1 and 2, single-crystal X-ray diffraction analysis. X-Ray diffraction discloses that complexes adopt tetranuclear tin(iv) ladder-like structures containing two (1) or four (2) deprotonated ligands. The essential difference between their molecular structures is that in 2 there are four carboxylate ligands, while in 1 and 3 there are two. The crystal structure of 1 reveals them to be a tetranuclear structure containing a three-rung-staircase Sn4O4 core. The Sn4O4 cluster consists of a ladder of four Sn2O2 units. For 2, the structure is a tetranuclear centrosymmetric dimer of an oxoditin unit having a central four-member ring. In this complex, the central Sn2O2 core is fused with two four-member and two six-member rings. In the structures, there are two types of tin ions arranged in distorted trigonal bipyramid geometry or octahedron geometry. A series of O–H⋯N, C–H⋯O, and C–H⋯π intermolecular hydrogen bonds in these complexes play an important function in the supramolecular, or two-dimensional network structures are formed by these interactions.","PeriodicalId":18146,"journal":{"name":"Main Group Metal Chemistry","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2022-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138536193","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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