Reaction of [η¹:η<superscript>5</superscript>-(R<subscript>2</subscript>NCH<subscript>2</subscript>CH<subscript>2</subscript>)C<subscript>2</subscript>B<subscript>9</subscript>H<subscript>10</subscript>]TaMe<subscript>3</subscript> with Isonitriles: Effects of Nitrogen Substituents on Product Formation.
In: Organometallics, Jg. 35 (2016-05-23), Heft 10, S. 1430-1439
Online
academicJournal
Zugriff:
Tantallacarborane trimethyl complexes show diverse reactivity patterns toward isonitriles. Reaction of [η¹:η5-(Me2NCH2CH2)C2B9H10]TaMe3 (1) with 1-adamantyl isonitrile (AdNC) led to the clean formation of an imido complex, [σ:η5-(MeNCH2CH2)C2B9H10]Ta(=NAd)(THF) (2) with elimination of methane and 2-methylpropene, whereas treatment of [η¹:η5-{(CH2)5NCH2CH2}C2B9H10]TaMe3 (3) with AdNC under the same reaction conditions gave the cage B-H activated product {σ:η¹:η5-[(CH2)5NCHCH2](CHMe2)C2B9H9}Ta(=NAd)(THF) (4). An equimolar reaction of 1 with R¹NC (R¹ = Cy, Ad), followed by 1 equiv of R²NC (R² = Xyl, Cy), afforded the imido amido complexes [η¹:η5-(Me2NCH2CH2)C2B9H10]Ta(=NR¹)[N(CMe=CMe2)R²] (R¹ = Ad, R² = Cy (5); R¹ = Cy, R² = Xyl (6)). If 2 equiv of 2,6-dimethylphenyl isonitrile (XylNC) was used in the above reaction, the cage B-H alkylation products [η¹:η5-(Me2NCH2CH2)C2 B9H9]Ta(=NR¹)[N(Xyl){ CHC(Me2)C(Me)=NXyl}] (R¹ = Cy (7), Ad (8)) were isolated. On the other hand, η²-iminoacyl imido complexes [η¹:η5-(Me2NCH2CH2)(CHMe2)C2B9H9]Ta(=NXyl)(η²-C,N-MeC=NR) (R = iPr (9), Cy (10)) were obtained from an equimolar reaction of 1 with XylNC, followed by 1 equiv of alkyl isonitriles. A double methyl migratory insertion tantallaaziridine species is proposed as a crucial intermediate for all aforementioned reactions, and follow-up steps are dependent upon N-substituents and the type and stoichiometry of isonitriles. All new complexes were characterized by spectroscopic methods and single-crystal X-ray analyses. [ABSTRACT FROM AUTHOR]
Titel: |
Reaction of [η¹:η<superscript>5</superscript>-(R<subscript>2</subscript>NCH<subscript>2</subscript>CH<subscript>2</subscript>)C<subscript>2</subscript>B<subscript>9</subscript>H<subscript>10</subscript>]TaMe<subscript>3</subscript> with Isonitriles: Effects of Nitrogen Substituents on Product Formation.
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Autor/in / Beteiligte Person: | Xiang, Li ; Xie, Zuowei |
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Zeitschrift: | Organometallics, Jg. 35 (2016-05-23), Heft 10, S. 1430-1439 |
Veröffentlichung: | 2016 |
Medientyp: | academicJournal |
ISSN: | 0276-7333 (print) |
DOI: | 10.1021/acs.organomet.6b00053 |
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