116783-71-2

Upstream product

• 1079-66-9 chloro-diphenylphosphine 
• 56-34-8 tetraethylammonium chloride 
• 22560-16-3 lithium triethylborohydride 
• 80612-33-5 {N(C₂H₅)4}⁽¹⁺⁾*{HFe(CO)3(P(C₆H₅)3)}^(1-)={N(CH₂CH₃)4}{HFe(CO)3(P(C₆H₅)3)} 
• 26024-88-4 [Et₄N]₂[Fe₂(CO)₈] 

Downstream Products

• 1330185-48-2 [Fe2(CO)6(μ-CO)(μ-PPh2)(μ-Au(PPh2C6H4COO(CH2)11SH)] 
• 116783-83-6 (Et4N)(Fe2(CO)6(PPh3)2(μ-PPh2)) 
• 116839-31-7 (Et4N)(Fe2(CO)6(P(OMe)3)2(μ-PPh2)) 

Relevant academic research and scientific papers

Anionic and neutral spiked triangle clusters of mercury: a comparative study of the metal ligand redistribution process

The action of the NEt4+ salts of the anions 2- and - on ClHg-m complexes (m = Mo(CO)3Cp, W(CO)3Cp, Mn(CO)5, Co(CO)4, and Fe(CO)2Cp) has been investigated.In the first case, anionic spiked triangle clusters of formula - were obtained in high yields, and no metal ligand redistribution reactions were detected.However, the action of - on the same bimetallic transition metal-mercury compounds gave the neutral species , which spontaneously redistributed to 2> and m2Hg.Only the molybdenum derivative could be isolated in pure form.The different behaviour of the two series of complexes in the redistribution process is discussed.

Diferrate [Fe2(CO)6(μ-CO){μ-P(aryl)2}]? as Self-Assembling Iron/Phosphor-Based Catalyst for the Hydrogen Evolution Reaction in Photocatalytic Proton Reduction—Spectroscopic Insights

This work is focused on the identification and investigation of the catalytically relevant key iron species in a photocatalytic proton reduction system described by Beller and co-workers. The system is driven by visible light and consists of the low-cost [Fe3(CO)12] as catalyst precursor, electron-poor phosphines P(R)3 as co-catalysts, and a standard iridium-based photosensitizer dissolved in a mixture of THF, water, and the sacrificial reagent triethylamine. The catalytic reaction system was investigated by operando continuous-flow FTIR spectroscopy coupled with H2 gas volumetry, as well as by X-ray absorption spectroscopy, NMR spectroscopy, DFT calculations, and cyclic voltammetry. Several iron carbonyl species were identified, all of which emerge throughout the catalytic process. Depending on the applied P(R)3, the iron carbonyl species were finally converted into [Fe2(CO)6(μ-CO){μ-P(R)2}]?. This involves a P?C cleavage reaction. The requirements of P(R)3 and the necessary reaction conditions are specified. [Fe2(CO)6(μ-CO){μ-P(R)2}]? represents a self-assembling, sulfur-free [FeFe]-hydrogenase active-site mimic and shows good catalytic activity if the substituent R is electron poor. Deactivation mechanisms have also been investigated, for example, the decomposition of the photosensitizer or processes observed in the case of excessive amounts of P(R)3. [Fe2(CO)6(μ-CO){μ-P(R)2}]? has potential for future applications.

Synthesis and reactions of the [(μ-Ph2P)Fe2(CO)6]- anion

The action of 2 molar equiv of LiBEt3H on (μ-CH3C=O)(μ-Ph2P)Fe2(CO)6 gives a reactive species which IR spectroscopic evidence suggests to be Li[(μ-Ph2P)Fe2(CO)6]. This species reacts with acid halides, RC(O)Cl, Me2NC(S)Cl, Me2P(S)Cl, and chlorophosphines; neutral products of type (μ-E)(μ-Ph2P)Fe2(CO)6 (E = RC=O, Me2NO=S, Me2P=S, R2P) were obtained in good yield. Reaction with CS2 and RNCS gave anionic products, (μ-S?C=S)(μ-Ph2P)Fe2(CO)6 and (μ-RN?C=S)(μ-Ph2P)Fe2(CO)6. The [(μ-Ph2P)Fe2(CO)6]-reagent is much more reactive than the known [(μ-CO)(μ-Ph2P)Fe2(CO)6]-. The structure of (μ-CH3)2P=S)(μ-PhS)Fe2(CO)6 (18b) has been determined by X-ray techniques. Compound 18b crystallizes in the orthorhombic space group P212121 with a = 12.494 (2) A?, b = 17.075 (2) A?, c = 8.7909 (9) A?, V = 1944.7 (7) A?3, and Z = 4. The two Fe(CO)3 groups in the complex are bridged by the benzenethiolate and the dimethylphosphino sulfide groups, the latter of which is S-bound to one metal and P-bound to the other. Within the SPMe2 ligand the P - S distance of 2.030 (2) A? lies intermediate between that of a single (2.18 A?) and a double (1.95 A?) bond.

Tricarbonyl(phosphine)ferrates(2-), Fe(CO)3(PR3)2-, and their derivatives

A two-step synthesis of K2[Fe(CO)3(PR3)] (PR3 = PPh3, PMe2Ph, and PMe3) from the corresponding Fe(CO)4(PR3) has been developed. Treatment of Fe(CO)4(PR3) with a methanolic solution of [Et4N]OH provided the corresponding monohydrides HFe(CO)3(PR3)-. Deprotonation of monohydrides by K[sec-Bu3BH] in refluxing tetrahydrofuran gave 50-70% isolated yields (based on Fe(CO)4(PR3)) of the thermally stable but exceedingly air-sensitive salts K2[Fe(CO)3(PR3)], which were characterized by elemental analysis, infrared spectra, and reactivity patterns. These are the first isolated salts containing (phosphine)-carbonylmetalate dianions and are extremely reactive. They quickly deprotonated acetonitrile to give essentially quantitative yields of HFe(CO)3(PR3)- and reacted with triphenylstannyl chloride to provide Ph3SnFe(CO)3(PR3)-. Ligand exchange reactions of K2[Fe(CO)3(PPh3)] with CO and P(OMe)3 readily occurred at room temperature and gave 80-90% isolated yields of K2[Fe(CO)4] and K2[Fe(CO)3(P(OMe)3)]. The latter salt contains the first isolated (phosphite)carbonylmetalate dianion and was characterized by elemental analyses and infrared spectra as a triphenyltin derivative, (Ph3Sn)Fe(CO)3(P(OMe)3)-. Treatment of [Et4N][HFe(CO)3(PPh3)] with hot ethanol provided low yields (ca. 10%) of the bridging phosphide salt [Et4N][Fe2(CO)6(μ-CO)(μ-PPh 2)]. Full details on the molecular structure of this anion, which has been mentioned previously in the scientific literature (Kyba, E. P.; Davis; R. E.; Clubb, C. N.; Liu, S. T.; Palacios, H. A. O.; McKennis, J. S., Organometallics 1986, 5, 869), are reported for the first time. Crystal data: triclinic, space group P1 (No. 2); a = 11.140 (1) A?, b = 1-3.982 (4) A?, c = 10.161 (3) A?; α = 105.30 (2)°, β = 103.33 (2)°, γ = 77.21 (2)°, V = 1464 (1) A?3; Z = 2; R = 0.034; Rw = 0.039.