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Isolation of [Ru(IPr)2(CO)H]+ (IPr = 1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene) and Reactivity toward E–H (E = H, B) Bonds
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dc.contributor.author | Riddlestone, Ian M. | |
dc.contributor.author | McKay, David | |
dc.contributor.author | Gutmann, Matthias J. | |
dc.contributor.author | Macgregor, Stuart A. | |
dc.contributor.author | Mahon, Mary F. | |
dc.contributor.author | Sparkes, Hazel A. | |
dc.contributor.author | Whittlesey, Michael K. | |
dc.date.accessioned | 2017-04-26T23:33:54Z | |
dc.date.available | 2017-04-26T23:33:54Z | |
dc.date.issued | 2016-05-09 | |
dc.identifier | 242705706 | |
dc.identifier | 544d3fc2-9b4f-4d1f-976f-3f59651e1129 | |
dc.identifier | 84969700135 | |
dc.identifier | 000375887300015 | |
dc.identifier.citation | Riddlestone , I M , McKay , D , Gutmann , M J , Macgregor , S A , Mahon , M F , Sparkes , H A & Whittlesey , M K 2016 , ' Isolation of [Ru(IPr) 2 (CO)H] + (IPr = 1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene) and Reactivity toward E–H (E = H, B) Bonds ' , Organometallics , vol. 35 , no. 9 , pp. 1301-1312 . https://doi.org/10.1021/acs.organomet.6b00173 | en |
dc.identifier.issn | 0276-7333 | |
dc.identifier.other | RIS: urn:49920ED960F55B54EA21524A3D74C9B8 | |
dc.identifier.other | ORCID: /0000-0003-0362-7848/work/29608111 | |
dc.identifier.uri | https://hdl.handle.net/10023/10668 | |
dc.description | Experiments at the ISIS Pulsed Neutron and Muon Source were supported by a beamtime allocation (Experiment 1510181) from the Science and Technology Facilities Council (STFC). The EPSRC (grants EP/J009962/1 and EP/J010677/1) is thanked for financial support. | en |
dc.description.abstract | Halide abstraction from the ruthenium N-heterocyclic carbene complex Ru(IPr)2(CO)HCl (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) with NaBAr4F (BAr4F = B{C6H3(3,5-CF3)2}4) gave the salt [Ru(IPr)2(CO)H]BAr4F ( 2 ), which was shown through a combined X-ray/neutron structure refinement and quantum theory of atoms in molecules (QTAIM) study to contain a bifurcated Ru···η3-H2C ξ-agostic interaction involving one iPr substituent of the IPr ligand. This system complements the previously reported [Ru(IMes)2(CO)H]+ cation (IMes =1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), where a non-agostic form is favored. Treatment of 2 with CO, H2, and the amine–boranes H3B·NR2H (R = Me, H) gave [Ru(IPr)2(CO)3H]BAr4F ( 3 ), [Ru(IPr)2(CO)(η2-H2)H]BAr4F ( 4 ), and [Ru(IPr)2(CO)(κ2-H2BH·NR2H)H]BAr4F (R = Me, 5 ; R = H, 6 ), respectively. Heating 5 in the presence of Me3SiCH═CH2 led to alkene hydroboration and formation of the C–H activated product [Ru(IPr)(IPr)′(CO)]BAr4F ( 7 ). X-ray characterization of 3 and 5 – 7 was complemented by DFT calculations, and the mechanism of H2/H exchange in 4 was also elucidated. Treatment of 2 with HBcat resulted in Ru–H abstraction to form the boryl complex [Ru(IPr)2(CO)(Bcat)] BAr4F ( 8 ), which proved to be competent in the catalytic hydroboration of 1-hexene. In 8 , a combined X-ray/neutron structure refinement and QTAIM analysis suggested the presence of a single Ru···η2-HC ξ-agostic interaction. | |
dc.format.extent | 12 | |
dc.format.extent | 1275813 | |
dc.language.iso | eng | |
dc.relation.ispartof | Organometallics | en |
dc.subject | QD Chemistry | en |
dc.subject | DAS | en |
dc.subject.lcc | QD | en |
dc.title | Isolation of [Ru(IPr)2(CO)H]+ (IPr = 1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene) and Reactivity toward E–H (E = H, B) Bonds | en |
dc.type | Journal article | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.identifier.doi | 10.1021/acs.organomet.6b00173 | |
dc.description.status | Peer reviewed | en |
dc.date.embargoedUntil | 2017-04-26 | |
dc.identifier.url | http://pubs.acs.org/doi/suppl/10.1021/acs.organomet.6b00173 | en |
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