337380-82-2

Basic information

• Product Name: Fe₂(CO)5(P(CH₂CH₂CN)3)(HCCHC₆H₅)P(C₆H₅)2
• CAS NO: 337380-82-2
• Molecular Weight: 733.263
• Mol File: 337380-82-2.mol
• Article Data: 1

Chemical Properties

• CAS DataBase Reference: Fe₂(CO)5(P(CH₂CH₂CN)3)(HCCHC₆H₅)P(C₆H₅)2(CAS DataBase Reference)
• NIST Chemistry Reference: Fe₂(CO)5(P(CH₂CH₂CN)3)(HCCHC₆H₅)P(C₆H₅)2(337380-82-2)
• EPA Substance Registry System: Fe₂(CO)5(P(CH₂CH₂CN)3)(HCCHC₆H₅)P(C₆H₅)2(337380-82-2)

Safety Data

• Hazardous Substances Data: 337380-82-2(Hazardous Substances Data)

Upstream product

• 4023-53-4 tris(2-cyanoethyl)phosphine 

Relevant articles and documents

α-β Alkenyl isomerisation at diiron centres

α-Substituted alkenyl complexes [Fe2(CO)6(μ-RC=CH2)(μ-PPh2)] 1a-1e (R=Ph, Me, n-Pr, n-Bu or t-Bu) have been prepared via regioselective hydrodimetallation of primary alkynes by [Fe2H(CO)7(μ-PPh2)]. Thermolysis in toluene results in isomerisation to the β-substituted complexes [Fe2(CO)6(μ-HC=CHR)(μ-PPh2)] 2a-2e. Isomerisation is accelerated in the presence of a range of tertiary phosphines yielding [Fe2(CO)5(PR'3)(μ-HC=CHR)(μ-PPh2)] 3a-3j in which the phosphine is coordinated to the ?-bound metal centre and lies trans to the phosphido-bridge. Addition of trimethyl phosphite to [Fe2(CO)6(μ-PhC=CH2)(μ-PPh2)] 1a at 60-70 deg C affords mono- and di-substituted α-alkenyl complexes [Fe2(CO)5{P(OMe)3}(μ-PhC=CH2)(μ-PPh2)] 4 and [Fe2(CO)4{P(OMe)3}(μ-PhC=CH2)(μ-PPh2)] 5 respectively. Above 100 deg C, conversion into β-substituted isomers [Fe2(CO)5{P(OMe)3}(μ-HC=CHPh)(μ-PPh2)] 6 and [Fe2(CO)4{P(OMe)3}2(μ-HC=CHPh)(μ-PPh2)] 7 occurs cleanly. Crystallographic studies have been carried out on 1a, [Fe2(CO)6(μ-n-PrC=CH2)(μ-PPh2)] 1c, [Fe2(CO)6(μ-HC=CHPh)(μ-PPh2)] 2a, [Fe2(CO)5(PPh3)(μ-HC=CHPh)(μ-PPh2)] 3a, 6 and 7 and compared with related structures. Different structural characteristics are seen between isomers, β isomers being characterised by a longer Fe?-Cβ interaction and a more obtuse Fe?-Cα-Cβ angle. The mechanisms of alkyne addition to [Fe2H(CO)7(μ-PPh2)] and alkenyl isomerisation have been probed using PhC2D. Hydrodimetallation results in an equal distribution of the deuterium over both β sites in 1a, and since they do not in exchange on the NMR timescale suggests that a radical process in operating. Thermolysis of this mixture leads to a 3:1 mixture of [Fe2(CO)6(μ-DC=CHPh)(μ-PPh2)] 2a-d1α and [Fe2(CO)6(μ-HC=CDPh)(μ-PPh2)] 2a-d1β. A mechanism for α-β alkenyl isomerisation is proposed in which oxidative additions of the trans (exo) and cis (endo) β-protons to terminal sites on the diiron centre, giving a parallel alkyne intermediate, are in competition.