Source:http://linkedlifedata.com/resource/pubmed/id/16608344
| Subject | Predicate | Object | Context |
|---|---|---|---|
| pubmed-article:16608344 | rdf:type | pubmed:Citation | lld:pubmed |
| pubmed-article:16608344 | lifeskim:mentions | umls-concept:C0002078 | lld:lifeskim |
| pubmed-article:16608344 | lifeskim:mentions | umls-concept:C0220781 | lld:lifeskim |
| pubmed-article:16608344 | lifeskim:mentions | umls-concept:C1883254 | lld:lifeskim |
| pubmed-article:16608344 | lifeskim:mentions | umls-concept:C1880022 | lld:lifeskim |
| pubmed-article:16608344 | lifeskim:mentions | umls-concept:C0205088 | lld:lifeskim |
| pubmed-article:16608344 | pubmed:issue | 15 | lld:pubmed |
| pubmed-article:16608344 | pubmed:dateCreated | 2006-4-12 | lld:pubmed |
| pubmed-article:16608344 | pubmed:abstractText | Reactions of LAl with ethyne, mono- and disubstituted alkynes, and diyne to aluminacyclopropene LAl[eta2-C2(R1)(R2)] ((L = HC[(CMe)(NAr)]2, Ar = 2,6-iPr2C6H3); R1 = R2 = H, (1); R1 = H, R2 = Ph, (2); R1 = R2 = Me, (3); R1 = SiMe3, R2 = C[triple bond]CSiMe3, (4)) are reported. Compounds 1 and 2 were obtained in equimolar quantities of the starting materials at low temperature. The amount of C2H2 was controlled by removing an excess of C2H2 in the range from -78 to -50 degrees C. Compound 4 can be alternatively prepared by the substitution reaction of LAl[eta2-C2(SiMe3)2] with Me3SiC[triple bond]CC[triple bond]CSiMe3 or by the reductive coupling reaction of LAlI2 with potassium in the presence of Me3SiC[triple bond]CC[triple bond]CSiMe3. The reaction of LAl with excess C2H2 and PhC[triple bond]CH (<1:2) afforded the respective alkenylalkynylaluminum compounds LAl(CH=CH2)(C[triple bond]CH) (5) and LAl(CH=CHPh)(C[triple bond]CPh) (6). The reaction of LAl(eta2-C2Ph2) with C2H2 and PhC[triple bond]CH yielded LAl(CPh=CHPh)(C[triple bond]CH) (7) and LAl(CPh=CHPh)(C[triple bond]CPh) (8), respectively. Rationally, the formation of 5 (or 6) may proceed through the corresponding precursor 1 (or 2). The theoretical studies based on DFT calculations show that an interaction between the Al(I) center and the C[triple bond]C unit needs almost no activation energy. Within the AlC2 ring the computational Al-C bond order of ca. 1 suggests an Al-C sigma bond and therefore less pi electron delocalization over the AlC2 ring. The computed Al-eta2-C2 bond dissociation energies (155-82.6 kJ/mol) indicate a remarkable reactivity of aluminacyclopropene species. Finally, the 1H NMR spectroscopy monitored reaction of LAl(eta2-C2Ph2) and PhC[triple bond]CH in toluene-d8 may reveal an acetylenic hydrogen migration process. | lld:pubmed |
| pubmed-article:16608344 | pubmed:language | eng | lld:pubmed |
| pubmed-article:16608344 | pubmed:journal | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16608344 | pubmed:status | PubMed-not-MEDLINE | lld:pubmed |
| pubmed-article:16608344 | pubmed:month | Apr | lld:pubmed |
| pubmed-article:16608344 | pubmed:issn | 0002-7863 | lld:pubmed |
| pubmed-article:16608344 | pubmed:author | pubmed-author:RoeskyHerbert... | lld:pubmed |
| pubmed-article:16608344 | pubmed:author | pubmed-author:SchmidtHans-G... | lld:pubmed |
| pubmed-article:16608344 | pubmed:author | pubmed-author:NoltemeyerMat... | lld:pubmed |
| pubmed-article:16608344 | pubmed:author | pubmed-author:HosmaneNaraya... | lld:pubmed |
| pubmed-article:16608344 | pubmed:author | pubmed-author:MaQingjunQ | lld:pubmed |
| pubmed-article:16608344 | pubmed:author | pubmed-author:YangZhiZ | lld:pubmed |
| pubmed-article:16608344 | pubmed:author | pubmed-author:ZhuHongpingH | lld:pubmed |
| pubmed-article:16608344 | pubmed:author | pubmed-author:FanHongjunH | lld:pubmed |
| pubmed-article:16608344 | pubmed:author | pubmed-author:OswaldRainer... | lld:pubmed |
| pubmed-article:16608344 | pubmed:author | pubmed-author:StarkeKerstin... | lld:pubmed |
| pubmed-article:16608344 | pubmed:issnType | lld:pubmed | |
| pubmed-article:16608344 | pubmed:day | 19 | lld:pubmed |
| pubmed-article:16608344 | pubmed:volume | 128 | lld:pubmed |
| pubmed-article:16608344 | pubmed:owner | NLM | lld:pubmed |
| pubmed-article:16608344 | pubmed:authorsComplete | Y | lld:pubmed |
| pubmed-article:16608344 | pubmed:pagination | 5100-8 | lld:pubmed |
| pubmed-article:16608344 | pubmed:year | 2006 | lld:pubmed |
| pubmed-article:16608344 | pubmed:articleTitle | Aluminacyclopropene: syntheses, characterization, and reactivity toward terminal alkynes. | lld:pubmed |
| pubmed-article:16608344 | pubmed:affiliation | Institut für Anorganische Chemie der Universität Göttingen, Tammannstrasse 4, D-37077 Göttingen, Germany. | lld:pubmed |
| pubmed-article:16608344 | pubmed:publicationType | Journal Article | lld:pubmed |