1919884-90-4

Basic information

• Product Name: [Mn(HN(C₂H₄PⁱPr₂)₂)(CO)₂Br]
• CAS NO: 1919884-90-4
• Molecular Weight: 496.287
• Mol File: 1919884-90-4.mol
• Article Data: 7

Chemical Properties

• CAS DataBase Reference: [Mn(HN(C₂H₄PⁱPr₂)₂)(CO)₂Br](CAS DataBase Reference)
• NIST Chemistry Reference: [Mn(HN(C₂H₄PⁱPr₂)₂)(CO)₂Br](1919884-90-4)
• EPA Substance Registry System: [Mn(HN(C₂H₄PⁱPr₂)₂)(CO)₂Br](1919884-90-4)

Safety Data

• Hazardous Substances Data: 1919884-90-4(Hazardous Substances Data)

Usage

Description

[Mn(HN(C₂H₄PⁱPr₂)₂)(CO)₂Br] is a manganese pincer complex that plays a crucial role in the hydrogenation of various organic compounds, such as nitriles, ketones, and aldehydes. This complex is characterized by its unique structure, which includes a manganese atom coordinated to two carbonyl groups, a bromide ion, and a bis[(2-diisopropylphosphino)ethyl]amine ligand. The presence of these functional groups allows for efficient catalysis and selective hydrogenation reactions.

Uses

Used in Chemical Synthesis Industry:
[Mn(HN(C₂H₄PⁱPr₂)₂)(CO)₂Br] is used as a catalyst for hydrogenation reactions in the chemical synthesis industry. Its ability to selectively hydrogenate nitriles, ketones, and aldehydes makes it a valuable tool for the production of various chemicals and pharmaceuticals. The complex's high catalytic activity and selectivity contribute to more efficient and environmentally friendly synthetic processes.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, [Mn(HN(C₂H₄PⁱPr₂)₂)(CO)₂Br] is employed as a catalyst for the hydrogenation of key intermediates in the synthesis of various drugs. Its selectivity and efficiency in hydrogenation reactions enable the production of high-quality active pharmaceutical ingredients (APIs) with minimal by-products, ultimately leading to more effective and safer medications.
Used in Environmental Remediation:
[Mn(HN(C₂H₄PⁱPr₂)₂)(CO)₂Br] can also be utilized in environmental remediation processes, particularly for the treatment of wastewater containing toxic nitriles and other organic pollutants. The complex's ability to selectively hydrogenate these pollutants into less harmful compounds can help reduce the environmental impact of industrial effluents and contribute to cleaner water sources.

Upstream product

• 131890-26-1 bis[2-(di-iso-propylphosphino)ethyl]amine 
• 14516-54-2 bromopentacarbonylmanganese(I) 

Relevant articles and documents

The synthesis of PNP-supported low-spin nitro manganese(I) carbonyl complexes

The coordination chemistry of Mn(CO)5Br was investigated with a series of PNP-pincer ligands. The ligandsiPrPONOP (iPrPONOP?=?2,6-bis(diisopropylphosphinito)pyridine) andiPrPNHP (iPrPNHP?=?HN{CH2CH2(PiPr2)}2) gave the desired organometallic manganese complexes (iPrPONOP)Mn(CO)2Br and (iPrPNHP)Mn(CO)2Br, respectively, upon chelation to Mn(CO)5Br. The reactivity ofiPrPNNNP (iPrPNNNP?=?N,N′-bis(diisopropylphosphino)-2,6-diaminopyridine) with Mn(CO)5Br yielded a pair of products, [(iPrPNNNP)Mn(CO)3][Br] and (iPrPNNNCO)Mn(CO)3. The formation of the asymmetric chelate arises from a formal loss of iPr2PBr and C–N bond formation from a carbonyl ligand and NH, yielding a Mn(I) amide core. The nitration reactions of (iPrPONOP)Mn(CO)2Br and (iPrPNHP)Mn(CO)2Br were carried out using silver nitrite, yielding the nitro compounds (iPrPONOP)Mn(CO)2(NO2) and (iPrPNHP)Mn(CO)2(NO2), respectively. The analogous iron complex (iPrPONOP)Fe(CO)Cl2was nitrated under the same conditions to yield the salt pair [(iPrPONOP)Fe(CO)2][FeCl3NO]. This reactivity underlines the difference between iso-valent iron and manganese centers. The manganese complexes (iPrPONOP)Mn(CO)2(NO2) and (iPrPNHP)Mn(CO)2(NO2) were ineffective as oxygen atom transfer reagents for a variety of substrates.

Catalytic Hydrogenation of Cyclic Carbonates using Manganese Complexes

Catalytic hydrogenation of cyclic carbonates to diols and methanol was achieved using a molecular catalyst based on earth-abundant manganese. The complex [Mn(CO)2(Br)[HN(C2H4PiPr2)2] 1 comprising commercially available MACHO ligand is an effective pre-catalyst operating under relatively mild conditions (T=120 °C, p(H2)=30–60 bar). Upon activation with NaOtBu, the formation of coordinatively unsaturated complex [Mn(CO)2[N(C2H4PiPr2)2)] 5 was spectroscopically verified, which confirmed a kinetically competent intermediate. With the pre-activated complex, turnover numbers up to 620 and 400 were achieved for the formation of the diol and methanol, respectively. Stoichiometric reactions under catalytically relevant conditions provide insight into the stepwise reduction form the CO2 level in carbonates to methanol as final product.

Manganese-Catalyzed Upgrading of Ethanol into 1-Butanol

Biomass-derived ethanol is an important renewable feedstock. Its conversion into high-quality biofuels is a promising route to replace fossil resources. Herein, an efficient manganese-catalyzed Guerbet-type condensation reaction of ethanol to form 1-butanol was explored. This is the first example of upgrading ethanol into higher alcohols using a homogeneous non-noble-metal catalyst. This process proceeded selectively in the presence of a well-defined manganese pincer complex at the parts per million (ppm) level. The developed reaction represents a sustainable synthesis of 1-butanol with excellent turnover number (>110 000) and turnover frequency (>3000 h-1). Moreover, mechanistic studies including control experiments, NMR spectroscopy, and X-ray crystallography identified the essential role of the "N-H moiety" of the manganese catalysts and the major reaction intermediates related to the catalytic cycle.