期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 25, 期 62, 页码 14246-14252出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201903973
关键词
arsaethynolate; carbenes; decarbonylation; density functional calculations; uranium
资金
- UK EPSRC [EP/M027015/1, EP/P001286/1]
- ERC [CoG612724]
- Royal Society [UF110005]
- Leverhulme Trust [RF/2018-545\4]
- National Nuclear Laboratory
- University of Regensburg
- Deutsche Forschungsgemeinschaft
- COST Action [CM1006]
- National EPSRC UK EPR Facility
- University of Manchester
- EPSRC [EP/M027015/1] Funding Source: UKRI
Little is known about the chemistry of the 2-arsaethynolate anion, but to date it has exclusively undergone fragmentation reactions when reduced. Herein, we report the synthesis of [U(Tren(TIPS))(OCAs)] (2, Tren(TIPS)=N(CH(2)CH(2)NSiiPr(3))(3)), which is the first isolable actinide-2-arsaethynolate linkage. UV-photolysis of 2 results in decarbonylation, but the putative [U(Tren(TIPS))(As)] product was not isolated and instead only [{U(Tren(TIPS))}(2)(mu-eta(2):eta(2)-As2H2)] (3) was formed. In contrast, reduction of 2 with [U(Tren(TIPS))] gave the mixed-valence arsenido [{U(Tren(TIPS))}(2)(mu-As)] (4) in very low yield. Complex 4 is unstable which precluded full characterisation, but these photolytic and reductive reactions testify to the tendency of 2-arsaethynolate to fragment with CO release and As transfer. However, addition of 2 to an electride mixture of potassium-graphite and 2,2,2-cryptand gives [{U(Tren(TIPS))}(2){mu-eta(2)(OAs):eta(2)(CAs)-OCAs}][K(2,2,2-cryptand)] (5). The coordination mode of the trapped 2-arsaethynolate in 5 is unique, and derives from a new highly reduced and bent form of this ligand with the most acute O-C-As angle in any complex to date (O-C-As angle approximate to 128 degrees). The trapping rather than fragmentation of this highly reduced O-C-As unit is unprecedented, and quantum chemical calculations reveal that reduction confers donor-acceptor character to the O-C-As unit.
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