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Article: Cyclopentadienyl molybdenum(II) N,C-chelating benzothiazole-carbene complexes: Synthesis, structure, and application in cyclooctene epoxidation catalysis
Title | Cyclopentadienyl molybdenum(II) N,C-chelating benzothiazole-carbene complexes: Synthesis, structure, and application in cyclooctene epoxidation catalysis |
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Authors | |
Issue Date | 2014 |
Citation | Organometallics, 2014, v. 33, n. 10, p. 2457-2466 How to Cite? |
Abstract | A series of new benzothiazolyl-imidazolium salts 1-3 (1-(benzothiazol-2-yl) -3-methylimidazolium chloride (1); 1-(benzothiazol-2-yl)-3-benzylimidazolium chloride (2); 1-(benzothiazol-2-yl)-3-allylimidazolium chloride (3)) have been prepared from nucleophilic substitution of 2-chlorobenzothiazole by imidazoles. They serve as the precursors of hybrid N-heterocyclic carbene (NHC) ligands L1-L3 (L1 = 1-(benzothiazolin-2-yl)-3-methylimidazol-2-ylidene; L2 = 1-(benzothiazolin-2-yl)-3-benzylimidazol-2-ylidene; L3 = 1-(benzothiazolin-2-yl) -3-allylimidazol-2-ylidene). Reactions of 1-3 with Ag2O result in Ag(I) NHC complexes 4-6 [Ag(L)(μ-Cl)]2 (L = L1, 4; L = L2, 5) and Ag(L3)Cl (6), in which L1-L3 act as monodentate carbene ligand with a benzothiazolyl pendant. Subsequent transmetalation of 4-6 with CpMo(CO) 3Br (Cp = cyclopentadienyl) and anion exchange reaction with AgX (X = BF4, PF6, or OTf) give complexes [CpMo(CO) 2(L)]2[Ag2Br4] (L = L1, 7a; L = L2, 8a; L = L3, 9a) and [CpMo(CO)2(L)][X] (L = L1, X = BF4, 7b; L = L2, X = BF4, 8b; X = PF6, 8c; X = OTf, 8d; L = L3, X = BF4, 9b), whose structures are reported herein. The ligands L1-L3 show their versatility by switching to be N,C-chelating in these Mo(II) complexes. The chelation of the hybrid NHC ligand results in shorter Mo-C carbene bonds (2.14-2.16 Å) comparing with known Mo(II) NHC complexes in the literature. These complexes are active toward cyclooctene epoxidation with tert-butyl hydroperoxide (TBHP) affording up to 90% yield of epoxide (for 8b) in 3 h at 55 °C. © 2014 American Chemical Society. |
Persistent Identifier | http://hdl.handle.net/10722/219749 |
ISSN | 2023 Impact Factor: 2.5 2023 SCImago Journal Rankings: 0.654 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Wang, Zhe | - |
dc.contributor.author | Ng, Sin Wee Benny | - |
dc.contributor.author | Jiang, Lu | - |
dc.contributor.author | Leong, Wen Jin | - |
dc.contributor.author | Zhao, Jin | - |
dc.contributor.author | Hor, T. S Andy | - |
dc.date.accessioned | 2015-09-23T02:57:52Z | - |
dc.date.available | 2015-09-23T02:57:52Z | - |
dc.date.issued | 2014 | - |
dc.identifier.citation | Organometallics, 2014, v. 33, n. 10, p. 2457-2466 | - |
dc.identifier.issn | 0276-7333 | - |
dc.identifier.uri | http://hdl.handle.net/10722/219749 | - |
dc.description.abstract | A series of new benzothiazolyl-imidazolium salts 1-3 (1-(benzothiazol-2-yl) -3-methylimidazolium chloride (1); 1-(benzothiazol-2-yl)-3-benzylimidazolium chloride (2); 1-(benzothiazol-2-yl)-3-allylimidazolium chloride (3)) have been prepared from nucleophilic substitution of 2-chlorobenzothiazole by imidazoles. They serve as the precursors of hybrid N-heterocyclic carbene (NHC) ligands L1-L3 (L1 = 1-(benzothiazolin-2-yl)-3-methylimidazol-2-ylidene; L2 = 1-(benzothiazolin-2-yl)-3-benzylimidazol-2-ylidene; L3 = 1-(benzothiazolin-2-yl) -3-allylimidazol-2-ylidene). Reactions of 1-3 with Ag2O result in Ag(I) NHC complexes 4-6 [Ag(L)(μ-Cl)]2 (L = L1, 4; L = L2, 5) and Ag(L3)Cl (6), in which L1-L3 act as monodentate carbene ligand with a benzothiazolyl pendant. Subsequent transmetalation of 4-6 with CpMo(CO) 3Br (Cp = cyclopentadienyl) and anion exchange reaction with AgX (X = BF4, PF6, or OTf) give complexes [CpMo(CO) 2(L)]2[Ag2Br4] (L = L1, 7a; L = L2, 8a; L = L3, 9a) and [CpMo(CO)2(L)][X] (L = L1, X = BF4, 7b; L = L2, X = BF4, 8b; X = PF6, 8c; X = OTf, 8d; L = L3, X = BF4, 9b), whose structures are reported herein. The ligands L1-L3 show their versatility by switching to be N,C-chelating in these Mo(II) complexes. The chelation of the hybrid NHC ligand results in shorter Mo-C carbene bonds (2.14-2.16 Å) comparing with known Mo(II) NHC complexes in the literature. These complexes are active toward cyclooctene epoxidation with tert-butyl hydroperoxide (TBHP) affording up to 90% yield of epoxide (for 8b) in 3 h at 55 °C. © 2014 American Chemical Society. | - |
dc.language | eng | - |
dc.relation.ispartof | Organometallics | - |
dc.title | Cyclopentadienyl molybdenum(II) N,C-chelating benzothiazole-carbene complexes: Synthesis, structure, and application in cyclooctene epoxidation catalysis | - |
dc.type | Article | - |
dc.description.nature | link_to_subscribed_fulltext | - |
dc.identifier.doi | 10.1021/om401128z | - |
dc.identifier.scopus | eid_2-s2.0-84901400724 | - |
dc.identifier.volume | 33 | - |
dc.identifier.issue | 10 | - |
dc.identifier.spage | 2457 | - |
dc.identifier.epage | 2466 | - |
dc.identifier.eissn | 1520-6041 | - |
dc.identifier.isi | WOS:000336642600007 | - |
dc.identifier.issnl | 0276-7333 | - |