Synthesis of μ-Phosphido Diiron Complexes Having a P−H Bond:  Hydrophosphination of Phenylacetylene and Methyl Acrylate with the Cationic μ-Phosphido Diiron Complex

Sugiura, Junji; Kakizawa, Taeko; Hashimoto, Hisako; Tobita, Hiromi

doi:10.1021/om049000o

Cited by 20 publications

(19 citation statements)

References 28 publications

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“…The intermetallic distances in these compounds (ca. 2.58 Å) are consistent with the presence of a metal−metal single bond and are comparable to those measured for related cyclopentadienyl compounds having P and C atoms at the bridging positions, such as the phosphide-bridged complexes [Fe 2 Cp 2 {μ-P(CHCHPh)Ph}(μ-CO)(CO) 2 ]OTf and [Fe 2 Cp(μ-PMe 2 )(μ-CO)(CO) 4 ] (ca. 2.62 Å).…”

Section: Resultssupporting

confidence: 84%

“…The best and more reproducible yields were obtained when using THF as solvent and a temperature of 243 K, although the formation of 2d can be also accomplished in CH 2 Cl 2 . In any case, it should be noted that the above reactions differ substantially from previous synthetic procedures to prepare related diiron cations, these relying on decarbonylation or carbonylation reactions of phosphide-bridged precursors. , …”

Section: Resultsmentioning

confidence: 99%

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Synthesis and Decarbonylation Reactions of Diiron Cyclopentadienyl Complexes with Bent-Phosphinidene Bridges

et al. 2011

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The phosphinidene complexes [Fe2Cp2(μ-PR)(μ-CO)(CO)2] (Cp = η5-C5H5; R=Cy, Ph, Mes, Mes*; Mes = 2,4,6-C6H2Me3, Mes* = 2,4,6-C6H2 t Bu3) were readily prepared in high yields through a two-step procedure starting from the corresponding phosphine complexes [Fe2Cp2(μ-CO)2(CO)(PH2R)]. When R = Cy, Ph, Mes, the first step required the oxidation of the phosphine complex with 1 equiv of [FeCp2]BF4, this being followed by spontaneous dehydrogenation to yield the cationic phosphide complexes [Fe2Cp2(μ-PHR)(μ-CO)(CO)2]BF4, while the formation of the related PMes*H-bridged complex required a double oxidation of the corresponding neutral precursor in the presence of a deprotonating agent. In all cases the final step involved the deprotonation of the above cations with strong bases such as M(OH) (M = Na, K). Attempts to decarbonylate the above phosphinidene complexes by either thermolysis or photolysis in solution gave results strongly dependent on the nature of R. Thus, the photolysis of the cyclohexylphosphinidene complex gave a mixture of the clusters [Fe4Cp4(μ3-PCy)2(μ3-CO)(μ-CO)(CO)] (Fe−Fe distances 2.6115(7) and 2.5332(8) Å) and [Fe3Cp3(μ3-PCy)(μ-PCyH)(μ-CO)2], while the thermal decarbonylation of the mesitylphosphinidene complex in refluxing toluene gave the trinuclear derivative [Fe3Cp3(μ-PMes)(μ-PMesH)(μ-CO)2(CO)], having a trigonal phosphinidene ligand bridging two iron atoms (Fe−P = 2.161(8), 2.165(8) Å). The formation of all these compounds presumably involves the participation of the corresponding intermediate complex [Fe2Cp2(μ-PR)(μ-CO)2], a species likely to contain a trigonal (four-electron-donor) phosphinidene ligand, not detected. In contrast, the supermesitylphosphinidene complex undergoes a C( t Bu)−H oxidative addition to the P atom under mild thermal conditions to give the phosphine derivative [Fe2Cp2(μ-CO)2(CO){PH(CH2CMe2)C6H2 t Bu2}], while its photolysis gave a mixture of the above phosphine complex and the phosphide−hydride derivatives cis- and trans-[Fe2Cp2(μ-H){μ-P(CH2CMe2)C6H2 t Bu2}(CO)2], the latter resulting from the oxidative addition of a P−H bond to the dimetal center.

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Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 99%

Synthesis and Decarbonylation Reactions of Diiron Cyclopentadienyl Complexes with Bent-Phosphinidene Bridges

et al. 2011

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“…Unlike comparatively popular hydroamination, − hydrophosphination is not as well developed. Like hydroamination, many reported systems rely on precious metals, but earth-abundant metals for catalytic hydrophosphination have emerged in recent years. − Catalytic hydrophosphination is still thwarted by substrate under-representation for both the unsaturated component and phosphine. The limited commercial availability of phosphines compared to amines is doubtlessly a contributing factor.…”

Section: Introductionmentioning

confidence: 99%

Light-Driven, Zirconium-Catalyzed Hydrophosphination with Primary Phosphines

et al. 2018

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Catalytic hydrophosphination using [κ 5 -N,N,N,N,C-(Me 3 SiNCH 2 CH 2 ) 2 NCH 2 CH 2 NSiMe 2 CH 2 ]Zr (1) under photolysis substantially enhances activity and avails greater substrate scope. Quantitative conversions of alkenes to secondary phosphines are reached in as little as 20 min at ambient temperature with 1 under ultraviolet or visible irradiation. A larger class of unactivated alkenes are now facile substrates under photolysis conditions, and 1 can engage in a previously unknown tandem inter/intramolecular hydrophosphination of 1,4-pentadiene to give the heterocyclic phosphorinane product. Computational and spectroscopic data indicate that photoexcitation of 1 at a variety of wavelengths results in P n → Zr d charge transfer. This excitation appears to accelerate catalysis by promoting substrate insertion at the Zr−P bond based on experimental observations.

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“…Metal complexes featuring phosphido ligands have attracted interest due to their great potential as effective catalysts, especially in promoting the formation of P–P and P–C bonds , . Moreover, these compounds are also catalytically active in the dehydrocoupling of amino‐ and phosphino‐boranes, which represents a versatile process for H 2 storage applications .…”

Section: Introductionmentioning

confidence: 99%

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

et al. 2018

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We report the synthesis of the first series of terminal phosphido iron complexes supported by a -diketiminato ligand (Dippnacnac) and their catalytic activity in dehydrocoupling of secondary phosphines. Anionic and neutral mono-or diphosphido complexes were obtained from the reaction of [(Dippnacnac)FeCl 2 Li(dme) 2 ] with the R 2 PLi (R = iPr, tBu, Cy, Ph) phosphides by tuning the stoichiometric ratio, polarity of the solvent, and the bulkiness of the substituents at the P-atom. The structures of the synthesized compounds were determined by single-crystal X-ray diffraction, which revealed that the iron [a] Reports by Webster et al. [14,27,43,[98][99][100][101][102] on the use of an iron(II) -diketiminato pre-catalyst, [(Dippnacnac)Fe(CH 2 TMS)] for the hydrophosphination of unsaturated hydrocarbons and dehydrocoupling of primary and secondary phosphines postulated the formation of an intermediate terminal phosphido complex. In the case of hydrophosphination, the authors proposed that the active catalyst is a monomeric phosphido complex; however, the active species was isolated as a bridging complex, [(Dippnacnac)Fe(PRH(CH 2 ) 3 CH=CH 2 )] 2 . [27] Worth emphasizing is that this compound is not only the first -diketiminate iron complex bridged by phosphido groups, but also a perfect example highlighting the catalytic potential of lowcoordinate iron compounds. The hydrophosphination and dehydrocoupling processes are both ideally suited for the synthesis of novel P-containing compounds and their catalytic improvements will expand the access to functionalized phosphines, diphosphanes, and other P-containing derivatives.Recently, we have reported a new synthetic method to access iron(II) phosphanylphosphido complexes using as starting materials the -diketiminato complex [(Dippnacnac)FeCl 2 -Li(dme) 2 ] [103] and lithium salts of diphosphanes, R 2 P-P(SiMe 3 )Li (R = iPr, tBu). [104] Due to the propensity of the diphosphorus ligand to undergo P-P bond cleavage, these iron(II) phosphanylphosphido complexes have rather limited catalytic potential. Considering this limitation, we directed our attention to iron(II) complexes with phosphido R 2 P ligands. In this paper, we detail the syntheses, structures, and spectroscopic characterization of the first series of terminal phosphido Fe II complexes stabilized by -diketiminates. We also discuss their thermal stability and catalytic activity in promoting the dehydrocoupling of secondary phosphines. Reaction of [(Dippnacnac)FeCl 2 ] with Ph 2 PLi:To the suspension of [(Dippnacnac)FeCl 2 ] (0.272 g, 0.5 mmol) in 2.5 mL of solvent (tolu-Eur.

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Synthesis of μ-Phosphido Diiron Complexes Having a P−H Bond: Hydrophosphination of Phenylacetylene and Methyl Acrylate with the Cationic μ-Phosphido Diiron Complex

Cited by 20 publications

References 28 publications

Synthesis and Decarbonylation Reactions of Diiron Cyclopentadienyl Complexes with Bent-Phosphinidene Bridges

Synthesis and Decarbonylation Reactions of Diiron Cyclopentadienyl Complexes with Bent-Phosphinidene Bridges

Light-Driven, Zirconium-Catalyzed Hydrophosphination with Primary Phosphines

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

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