191608-88-5

Upstream product

• 12078-28-3 dicarbonylcyclopentadienyliodoiron(II) 
• 19493-09-5 Methylenetriphenylphosphorane 
• 41593-58-2 diphenylphosphineborane 

Downstream Products

• 1036029-93-2 CpFe(CO)(PMe₃)(PPh₂*BH₃) 
• 1036029-94-3 CpFe(PMe₃)2(PPh₂*BH₃) 

Relevant academic research and scientific papers

Iron-catalyzed dehydropolymerization: A convenient route to poly(phosphinoboranes) with molecular-weight control

The catalyst loading is the key to control the molecular weight of the polymer in the iron-catalyzed dehydropolymerization of phosphine-borane adducts. Studies showed that the reaction proceeds through a chain-growth coordination-insertion mechanism.

The inverse sandwich complex [(K(18-crown-6))2Cp][CpFe(CO) 2] - Unpredictable redox reactions of [CpFe(CO)2]I with the silanides Na[SiRtBu2] (R = Me, tBu) and the isoelectronic phosphanyl borohydride K[PtBu2BH3]

The dimeric iron carbonyl [CpFe(CO)2]2 and the iodosilanes tBu2RSiI were obtained from the reaction of [CpFe(CO)2]I with the silanides Na[SiRtBu2] (R = Me, tBu) in THF. By the reactions of [CpFe(CO)2]I and Na[SiRtBu2] (R = Me, tBu) the disilanes tBu2RSiSiRtBu2 (R = Me, tBu) were additionally formed using more than one equivalent of the silanide. In this context it should be noted that reduction of [CpFe(CO)2]2 with Na[SitBu3] gives the disilanes tBu3SiSitBu 3 along with the sodium ferrate [(Na(18-crown-6))2Cp] [CpFe(CO)2]. The potassium analogue [(K(18-crown-6)) 2Cp][CpFe(CO)2] (orthorhombic, space group Pmc2 1), however, could be isolated as a minor product from the reaction of [CpFe(CO)2]I with [K(18-crown-6)][PtBu2BH3]. The reaction of [CpFe(CO)2]2 with the potassium benzophenone ketyl radical and subsequent treatment with 18-crown-6 yielded the ferrate [K(18-crown-6)][CpFe(CO)2] in THF at room temperature. The crown ether complex [K(18-crown-6)][CpFe(CO)2] was analyzed using X-ray crystallography (orthorhombic, space group Pna21) and its thermal behaviour was investigated.

Synthesis and dehydrocoupling reactivity of iron and ruthenium phosphine-borane complexes

The Fe and Ru phosphine-borane complexes CpM(CO)2PPh 2?BH3 (1, M = Fe, 4, M = Ru) were synthesized utilizing the reaction of the phosphine-borane anion Li[PPh2? BH3] with the iodo complexes CpM(CO)2I. The Fe complex 1 reacted with PMe3 to yield CpFe(CO)(PMe3)(PPh 2?BH3) (2) and CpFe(PMe3) 2(PPh2?BH3) (3) whereas the Ru species 4 gave only CpRu(CO)(PMe3)(PPh2?BH3) (5). The complexes 1-5 were characterized by 1H, 11B, 13C and 31P NMR spectroscopy, MS, IR and X-ray crystallography for 1 to 4, and EA for 1, 2 and 4. The reactivity of 1 and 4 towards PPh2H?BH3 was explored. Although no stoichiometric reactions were detected under mild conditions, both 1 and 4 were found to function as dehydrocoupling catalysts to afford Ph2PH? BH2?PPh2?BH3 in the melt at elevated temperature (120 °C). The carbonyl Fe2(CO)9 also functioned as a dehydrocoupling catalyst under similar conditions. Complex 1 and Fe2(CO)9 represent the first reported active Fe complexes for the catalytic dehydrocoupling of phosphine-borane adducts. The Royal Society of Chemistry 2008.

Broadening the scope of ancillary phosphane-type ligands: A systematic comparison of PR3, PR2BH3-, and SiR3- and their chalcogen derivatives

This work describes a systematic experimental and theoretical study of the properties of two series of isoelectronic and largely isosteric ligands, namely PPh2Me, PPh2BH3-, and SiPh 2Me- and SPtBu3, SPrBu2BH 3-, and SSitBu3-. In addition, we have also investigated the oxo derivatives OPPh2BH3 - and OSiPh2Me-. Based on X-ray crystal structure determinations (Fe-CO and C-O bond lengths) as well as NMR [e.g. δ(13CO)] and IR [ν(CO)] spectroscopic investigations of the corresponding [CpFe(CO)2]+ complexes, we can conclude that, with respect to electron donor strength, phosphanyl borohydrides occupy an intermediate position between phosphanes (weakest donors) and silyl ligands (strongest donors). The same is true for the thio derivatives, although the differences are smaller. In the reaction with [CpFe(CO)2] +, the oxo derivative OPPh2BH3- transfers a hydride ion rather than forming a stable [CpFe(CO) 2(OPPh2BH3)] complex. The tendency to undergo hydride-transfer reactions was studied by density functional calculations for the series PtBu2BH3-, OPtBu2BH 3, and SPtBu2BH3-. The results reveal that OPtBu2BH3- is the strongest and SPtBu2BH3- the weakest hydride donor, in accordance with the experimental observations. Theoretical analysis indicates that the three derivatives PPh2Me, PPh2BH3 _, and SiPh2Me- are truly isolobal species despite variations in their charge distributions. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Reactions of cationic piano stool iron complexes containing phosphorus ligands with phosphorus ylide

Reactions of PF6- salts of cationic piano stool iron complexes with a phosphorus ylide, CH2PPh3, were examined. In the reaction of the dicarbonyl complex [Cp(CO)2FeL]+ (L = P(OMe)3, P(OEt)3, PPh2(OMe)), Cp(CO)LFe{C(O)CH=PPh3} is formed by the nucleophilic attack of the carbene carbon of CH2PPh3 on the carbonyl carbon of the complex. In contrast, the reaction of the monocarbonyl complex [Cp(CO)LFe{P(OR)3}]+ (L = P(OMe)3, R = Me; L = PMe3, R = Me; L = P(OEt)3, R = Et) yields Cp(CO)LFe{P(O)(OR)2} by the Arbuzov-like dealkylation reaction. [Cp(PMe3)2Fe{P(OMe)3}]+, having no CO ligand, also exhibits the Arbuzov-like dealkylation reaction under forced conditions. These results indicate that increasing the back donation ability from a central transition metal to a ligand induces a change in the reaction site from a carbonyl carbon in a CO ligand to an α-carbon in a phosphite ligand. In the reaction of [Cp(CO)2Fe{PPh2H}]+, proton abstraction from the PPh2H ligand takes place to give a phosphide complex Cp(CO)2FePPh2.