Diiron Carbonyl Complexes Bearing an N,C,S-Pincer Ligand: Reactivity toward Phosphines, Heterolytic Fe–Fe Cleavage, and Electrocatalytic Proton Reduction
| Autor: | Masakazu Hirotsu, Chiaki Tsuboi, Isamu Kinoshita, Kiyokazu Santo |
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| Rok vydání: | 2014 |
| Předmět: | |
| Zdroj: | Organometallics. 33:4260-4268 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om500558h |
| Popis: | The thiolate-bridged diiron carbonyl complex [{Fe(μ-PyBPT-κ3N,C,S)(CO)2}Fe(CO)3] (1) consists of two units, Fe(PyBPT)(CO)2 and Fe(CO)3, where the N,C,S-pincer ligand PyBPT is a doubly deprotonated form of 3′-(2″-pyridyl)-1,1′-biphenyl-2-thiol. The two Fe complex units are connected through a thiolate S atom, π coordination, and an Fe–Fe bond. Diiron complex 1 reacted with 1 equiv of dimethylphenylphosphine to form the CO substitution product [{Fe(μ-PyBPT-κ3N,C,S)(CO)2}Fe(CO)2(PMe2Ph)] (3) via the phosphine adduct [{Fe(μ-PyBPT-κ3N,C,S)(CO)2}Fe(CO)3(PMe2Ph)] (2), which has a polarized Fe–Fe bond. A further reaction of 3 with PMe2Ph produced the N,C,S-pincer iron(II) complex trans-[Fe(PyBPT-κ3N,C,S)(CO)(PMe2Ph)2] (4) and the iron(0) complex trans-[Fe(CO)3(PMe2Ph)2]. 1,2-Bis(diphenylphosphino)benzene (dppbz) abstracted the Fe(CO)3 unit from 1 to give the dimeric diiron(II,II) complex [{Fe(μ-PyBPT-κ3N,C,S)(CO)2}2] (7) and the iron(0) complex [Fe(CO)3(dppbz)]. The asymmetric bridging ligand PyBPT and coordinati... |
| Databáze: | OpenAIRE |
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