159474-55-2

Upstream product

• 12150-46-8 1,1'-bis-(diphenylphosphino)ferrocene 
• 10170-69-1 dimanganese decacarbonyl 
• 67-56-1 methanol 
• 14693-30-2 decacarbonylmanganeserhenium 

Relevant academic research and scientific papers

Twisting and Tilting 1,1′-Bis(dialkylphosphino)ferrocene Bound to Low Valent Tricarbonylmaganese(I to -I)

Recently we had reported the noninnocent behavior of 1,1′-bis(diphenylphosphino)ferrocene (dppf) in Fe(CO)3dppf [Ringenberg et al., Inorg. Chem., 2017, 56, 7501]. Moving to the left in the periodic table, HMn(CO)3(dRpf) where dRpf = dppf (1H) and 1,1′-bis(diisopropylphosphino)ferrocene (dippf) (2H) were synthesized. The hydride ligand was removed by protonation with [(Et2O)2H][B(ArF)4] ([B(ArF)4]- = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate), resulting in the rapid evolution of H2 followed by the formation of an Fe→Mn interaction. The reaction mechanism was determined by in situ IR experiments which show that directly following protonation both [1]+ and [2]+ offer an open manganese coordination site that allows for the formation of an intramolecular Fe→Mn dative bond. This process is significantly faster for [2]+ than for [1]+. The reduction chemistry as studied by cyclic voltammetry (CV) reveals that both complexes change from a distorted octahedral coordination with an Fe→Mn interaction to an open square-pyramidal configuration which is more stable for [1]0 than [2]0. Reoxidation of this square-pyramidal species proceeds more reversibly for 2 versus 1 due to the faster ferrocene ligand reorganization. The electrochemical mechanism was studied by in situ spectroscopic techniques, e.g., IR, UV-vis-NIR (near IR), and EPR spectroelectrochemistry (SEC) as well as by CV simulation. The new complexes described offer an exciting platform for the development of electrocatalysts for the reduction of CO2 to CO, or for proton reduction (2H+ + 2e- → H2).

Amine-oxide-mediated oxidative methanolysis of metal-metal bonds in [MM'(CO)10] (M = Mn, Re; M' = Re) and [Os3(CO)12]: Crystal structure of fac-[Re{OC(O)OMe}(CO)3(η2-dppf)]

The reaction of 1,1'-bis(diphenylphosphino)ferrocene (dppf) with a mixture of [MnRe(CO)10], MeOH and Me3NO afforded the complexes fac-[MnH(CO)3(η2-dppf)] and [Re2(μ-OMe)2(μ-dppf) (CO)6]. In the one-pot reaction of [Re2(CO)10] with Me3NO, MeOH and dppf, the major mononuclear Re species isolated was the CO2-inserted complex fac-[Re{OC(O)OMe}(CO)3(η2-dppf)], the crystal structure of which was determined. The coordination sphere of the rhenium atom is roughly octahedral, consisting of an oxygen atom from the methyl carbonate ligand, two phosphorus atoms from a chelating dppf ligand, and three carbon atoms from a facial arrangement of three terminally bonded carbonyls. Analogous Me3NO-mediated methoxylation reactions involving [Os3(CO)12] were also investigated. With a [Me3NO]:[Os3(CO)12] ratio of 2:1, the major product is [Os3(CO)10(μ-H)(μ-Ome)]. With three molar equivalents of Me3NO, significant quantities of [Os3(CO)10(μ-OMe)2] are also obtained. (C) 2000 Elsevier Science Ltd.