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Group 7 carbonyl complexes of a PNN-heteroscorpionate ligand
Valdivieso, Jorge P ; Erickson, Alexander N ; Gardinier, James R RSC Adv.,2024,14,31502-31516. DOI: 10.1039/D4RA05287K PubMed ID: 39372051
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Abstract: A series of rhenium and manganese carbonyl complexes of a heteroscorpionate ligand with an atypical N2P-donor set has been prepared to better understand their electronic and CO releasing properties. Thus, the ligand, pz2TTP, with an a,a-bis(pyrazol-1-yl)tolyl group decorated with an ortho-situated di(ptolyl)phosphanyl reacts with carbonyl group 17 reagents to give [fac-(k2 NP-pz2TTP)Re(CO)3Br], 1, and [fac-(k3 N2P-pz2TTP)M(CO)3](OTf = O3SCF3), 2-M (M = Re, Mn), if care is taken during the preparation of the manganeses derivative. When heated in CH3CN, 2-Mn slowly transforms to [fac,cis-(k3 N2P-pz2TTP) Mn(CO)2(NCCH3)](OTf), 3-Mn. In contrast, the corresponding 3-Re can only be prepared from 2-Re using Me3NO; pure 3-Mn can also be prepared by this method. Experimental and density functional calculations at the M06L/Def2-TZVP/PCM(CH3CN) level show that the replacement of a carbonyl with an acetonitrile solvent decreases the oxidation potential by around 0.8 V per carbonyl released, making decarbonylated species potent reductants. At the same time, the electronic spectrum broadens and undergoes a red-shift, making dicarbonyl complexes more susceptible to photo-initiated decarbonylation reactions than tricarbonyls. When 2-Mn or 3-Mn are irradiated in with 390 nm LED light in aerated solutions, [trans-Mn(pz2TTP = O)2](OTf)2, 4, along with insoluble manganese oxides are rapidly formed.
Purchased from AmBeed: 14516-54-2
CAS No. : | 14516-54-2 | MDL No. : | MFCD00049806 |
Formula : | C5BrMnO5 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | LOCZKKJCQVRJPQ-UHFFFAOYSA-M |
M.W : | 274.89 | Pubchem ID : | 10978692 |
Synonyms : |
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Signal Word: | Danger | Class: | 6.1 |
Precautionary Statements: | P261-P264-P270-P271-P280-P302+P352-P304+P340-P312-P330-P363-P403-P501 | UN#: | 3466 |
Hazard Statements: | H301-H311-H331 | Packing Group: | Ⅲ |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.