Mechanism of MTO Catalyzed Deoxydehydration of Diols to Alkenes Using Sacrificial Alcohols
Yazarlar (9)
Purdue University, Amerika Birleşik Devletleri
Doç. Dr. Ayşegül ŞENOCAK
Tokat Gaziosmanpaşa Üniversitesi, Türkiye
Nc State University, Amerika Birleşik Devletleri
Purdue University, Amerika Birleşik Devletleri
Purdue University, Amerika Birleşik Devletleri
Purdue University, Amerika Birleşik Devletleri
Purdue University, Amerika Birleşik Devletleri
Nc State University, Amerika Birleşik Devletleri
Purdue University, Amerika Birleşik Devletleri
| Makale Türü | Özgün Makale |
| Makale Alt Türü | SSCI, AHCI, SCI, SCI-Exp dergilerinde yayınlanan tam makale |
| Dergi Adı | Organometallics |
| Dergi ISSN | 0276-7333 Wos Dergi Scopus Dergi |
| Dergi Tarandığı Indeksler | SCI-Expanded |
| Dergi Grubu | Q4 |
| Makale Dili | İngilizce |
| Basım Tarihi | 06-2013 |
| Cilt No | 32 |
| Sayı | 11 |
| Sayfalar | 3210 / 3219 |
| DOI Numarası | 10.1021/om400127z |
| Özet |
| Catalytic deoxydehydration (DODH) of vicinal diols is carried out employing methyltrioxorhenium (MTO) as the catalyst and a sacrificial alcohol as the reducing agent. The reaction kinetics feature an induction period when MTO is added last and show zero-order in [diol] and half-order dependence on [catalyst]. The rate-determining step involves reaction with alcohol, as evidenced by a KIE of 1.4 and a large negative entropy of activation (ΔS‡ = -154 ± 33 J mol-1 K -1). The active form of the catalyst is methyldioxorhenium(V) (MDO), which is formed by reduction of MTO by alcohol or via a novel C-C bond cleavage of an MTO-diolate complex. The majority of the MDO-diolate complex is present in dinuclear form, giving rise to the [Re]1/2 dependence. The MDO-diolate complex undergoes further reduction by alcohol in the rate-determining step to give rise to a putative rhenium(III) diolate. The latter is the active species in DODH extruding stereoselectively trans-stilbene from (R,R)-(+)-hydrobenzoin to regenerate MDO and complete the catalytic cycle. © 2013 American Chemical Society. |
| Anahtar Kelimeler |
BM Sürdürülebilir Kalkınma Amaçları
| Atıf Sayıları | |
| SCOPUS | 75 |
| Google Scholar | 93 |