(η
            <sup>5</sup>
            ‐Cyclopentadienyl)Tricarbonylmanganese(I) Complexes

Kirk, Patrick N.; Castellani, Michael P.; Rizzo, Michael J.; Atwood, Jim D.

doi:10.1002/9781118744994.ch13

Cited by 8 publications

(4 citation statements)

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“…The lithium salts LiCp tet and LiCp* were prepared by addition of 1 equiv of n -BuLi (0.25 M in hexane) to 1 M solution of Cp tet H (1 g, 0.008 mol) or Cp*H (5 mL, 0.0319 mol, distilled prior to use) in hexane at −78 °C, stirred overnight, and subsequently filtered and washed with hexane in a glovebox and dried (80% yield both cases). The following compounds were prepared according to literature: 1 ·(C 6 H 6 ) 2 ; (Tp)Mn(CO) 3 (Tp = trispyrazolyl borate), Cp tet Mn(CO) 3 , and Cp*Mn(CO) 3 were prepared using (py) 2 Mn(CO) 3 Br as the manganese synthon; tris(1-pyrazolyl)methane (Tpm), tris(3,5-dimethyl-1-pyrazoyl)methane (Tpm*), [(Tpm)Mn(CO) 3 ]OTf, and [(Tpm*)Mn(CO) 3 ]OTf; (bipy)Mn(CO) 3 Br and (phen)Mn(CO) 3 Br and (phen)Mn(CO) 3 Br. , …”

Section: Methodsmentioning

confidence: 99%

Photochemical Water-Splitting with Organomanganese Complexes

et al. 2017

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Certain organometallic chromophores with water-derived ligands, such as the known [Mn(CO)(μ-OH)] (1) tetramer, drew our attention as possible platforms to study water-splitting reactions. Herein, we investigate the UV irradiation of various tricarbonyl organomanganese complexes, including 1, and demonstrate that dihydrogen, CO, and hydrogen peroxide form as products in a photochemical water-splitting decomposition reaction. The organic and manganese-containing side products are also characterized. Labeling studies with O-1 suggest that the source of oxygen atoms in HO originates from free water that interacts with 1 after photochemical dissociation of CO (1-CO) constituting the oxidative half-reaction of water splitting mediated by 1. Hydrogen production from 1 is the result of several different processes, one of which involves the protons derived from the hydroxido ligands in 1 constituting the reductive half-reaction of water splitting mediated by 1. Other processes that generate H are also operative and are described. Collectively the results from the photochemical decomposition of 1 provide an opportunity to propose a mechanism, and it is discussed within the context of developing new strategies for water-splitting reactions with organomanganese complexes.

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Section: Methodsmentioning

confidence: 99%

Photochemical Water-Splitting with Organomanganese Complexes

et al. 2017

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“…Potassium pentamethylcyclopentadienide (KC 5 Me 5 ) is synthesized by a literature route. 7 1 H and 13 C NMR chemical shifts are reported in ppm relative to SiMe 4 (δ 0) and are referenced internally to the residual 1 H NMR resonance (δ 7.15 for C 6 D 5 H) or 13 C NMR resonance (δ 128.0 for C 6 D 6 ) of the solvent.…”

Section: General Proceduresmentioning

confidence: 99%

“…The IR spectrum of (η 5 -C 5 Me 5 ) 2 MoCl 2 as a KBr disk shows peaks at 2959 (s), 2904 (vs), 1456 (vs), 1374 (vs), 1069 (m), 1019 (vs), 804 (w), 679 (w), 609 (w), and 415 (w) cm 1 . Its 1 H NMR spectrum in C 6 D 6 contains a singlet at δ 1.46, and its 13 * The checkers obtained yields of 55-61%. They also emphasize the need for using a wide-bore cannula to avoid losses during transfer of the MoCl 5 /THF suspension, which tends to clump.…”

Section: Propertiesmentioning

confidence: 99%