PH‐Functionalized Phosphenium Complexes [C5R5(OC)2 WP(H)R′] (R′ = tBu, sMes): Synthesis, Isomerization, and Transformation into Hydrido Complexes Containing a tBuP(H)OH Ligand

Malisch, Wolfgang; Hirth, Ulrich-Andreas; Grün, Klaus; Schmeußer, Martin; Fey, Oliver; Weis, Udo

doi:10.1002/anie.199525001

Cited by 21 publications

(3 citation statements)

References 17 publications

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“…Once the hydride-phosphido intermediate [Os(η 5 -C 5 H 5 )H(PPh 2 )(P i Pr 3 )] + is formed, the RO−H addition to the Os−phosphino bond affords [Os(η 5 -C 5 H 5 )H 2 {P(OR)Ph 2 }(P i Pr 3 )] + . Related additions of methanol and water across WP bonds have also been reported …”

Section: Resultsmentioning

confidence: 73%

Synthesis and Characterization of Mixed-Phosphine Osmium Polyhydrides: Hydrogen Delocalization in [OsH₅P₃]⁺ Systems

et al. 2001

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The hexahydrido complex OsH6(PiPr3)2 (1) reacts with PHPh2 to give molecular hydrogen and the tetrahydride OsH4(PHPh2)(PiPr3)2 (2). However, the formation of OsH2(PHPh2)2(PiPr3)2 (3) as a consequence of the substitution of a second hydrogen molecule from 2 by PHPh2 does not occur. The treatment of 2 with 1.0 equiv of PHPh2 in toluene at 80 °C leads after 3 days to OsH2(PHPh2)3(PiPr3) (4). The preparation of 3 requires the previous acidolysis of 2 with HBF4, which gives [OsH5(PHPh2)(PiPr3)2]BF4 (5). In contrast to 2, the addition of PHPh2 to 5 affords [OsH3(PHPh2)2(PiPr3)2]BF4 (6) and molecular hydrogen. Deprotonation of 6 with Et3N yields 3. The skeleton of the cation of 5 has been determined by X-ray diffraction. The configuration is consistent with a Y-shaped OsP3 disposition with the osmium atom in the common vertex. Complex 5 also reacts with methanol and water to give [OsH5{P(OMe)Ph2}(PiPr3)2]BF4 (7) and [OsH5{P(OH)Ph2}(PiPr3)2]BF4 (8), respectively. The addition of Et3N to 7 affords OsH4{P(OMe)Ph2}(PiPr3)2 (9). A theoretical study on the OsH5(PH3)3 + model complex reveals that although a static description is fully consistent with a classical pentahydride assignment, the formation of a dihydrogen is a very low energy costing process, on both thermodynamic and kinetic grounds. Thus, these polyhydride systems might be better described as possessing delocalized hydrogen atoms. A further QM/MM IMOMM study on the actual OsH5(PR3)+ systems indicates that the inclusion of bulky phosphine substituents plays a role against the stability of dihydrogen forms, because of the higher steric congestion of lower coordination number complexes arising from repulsions between bulky phosphines. Although IMOMM calculations improve significantly the agreement with experimental structures, they do not change the validity of the aforementioned statement concerning delocalization.

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Section: Resultsmentioning

confidence: 73%

Synthesis and Characterization of Mixed-Phosphine Osmium Polyhydrides: Hydrogen Delocalization in [OsH₅P₃]⁺ Systems

et al. 2001

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“…Primary phosphine complexes of transition metals are of interest in metal-mediated P−H bond functionalizations, − phosphido/phosphinidene formation, , and materials science. , The known methods of preparing these metal complexes require the use of preisolated primary phosphines, which are often highly air-sensitive toxic liquids and exhibit an intense unpleasant odor . By treating PH 2 Ph with [Ru II (Por)(CO)] [Por = porphyrinato(2−)], we previously isolated several primary arylphosphine complexes of ruthenium porphyrins .…”

mentioning

confidence: 99%

One-Pot Synthesis of Metal Primary Phosphine Complexes from OPCl₂R or PCl₂R. Isolation and Characterization of Primary Alkylphosphine Complexes of a Metalloporphyrin

Huang

Xie

et al. 2006

Inorg. Chem.

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“…A four-electron phosphido complex has a formal PM double bond and exhibits the reactivity expected for metal–element multiple bonds . The phosphenium ion complex, on the other hand, is formally electron deficient and electrophilic at P …”

Section: Introductionmentioning

confidence: 99%

Electrophilic Aromatic Substitution Reactions of a Tungsten-Coordinated Phosphirenyl Triflate

Jayaraman

Sterenberg

2014

Organometallics

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The phosphirenyl cation complex [W(CO)5{PC(Ph)C(Ph)}]+ (2) is formed by chloride abstraction from the chlorophosphirene complex [W(CO)5{P(Cl)C(Ph)C(Ph)}] (1) with excess AlCl3. The phosphirenyl triflate complex [W(CO)5{P(OSO2CF3)C(Ph)C(Ph)}] (3) is formed by reaction of the chlorophosphirene complex with AgOSO2CF3 and is in equilibrium with and typically reacts in the same fashion as the phosphirenyl cation. Reaction of 3 with diethylaniline or anisole leads to electrophilic aromatic substitution preferentially at the para position. Reaction with N,N-dimethyl-p-toluidine, in which the para position is blocked, leads to exclusive ortho substitution. The resulting 1,2-substituted arene can adopt a P,N bidentate coordination mode if a CO is removed from tungsten via photolysis. Compound 3 reacts with aromatic heterocycles thiophene, furan, and pyrrole, leading exclusively to substitution in the 2 position, with no evidence for P–S, P–O, or P–N bond formation. Reaction with indole led to substitution at the 3 position, also with no evidence for P–N bond formation. However, upon chromatographic purification, the substituted indole product decomposes into a disubstituted product, with W-coordinated phosphirenyl units at the 3 position and at N. Reaction with phenol and diphenyl amine led exclusively to P–O and P–N bond formation, with no evidence for aromatic substitution. Phosphine products can be removed via oxidation of W with I2, followed by displacement with bipyridine. A computational study shows that coordination to W(CO)5 greatly enhances electrophilicity at P in phosphenium ions, leading to the observed rapid electrophilic substitution reactions.

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PH‐Functionalized Phosphenium Complexes [C₅R₅(OC)₂ WP(H)R′] (R′ = tBu, sMes): Synthesis, Isomerization, and Transformation into Hydrido Complexes Containing a tBuP(H)OH Ligand

Abstract: The readily accessible P–H‐functionalized half‐sandwich phosphenium complexes 1a (R = tBu, sMes) are characterized by a high reactivity of the PH or the WP bond which is the basis for isomerization and addition reactions leading to the hydrido complexes 2 and 3. ◯ = H, Me.

Cited by 21 publications

References 17 publications

Synthesis and Characterization of Mixed-Phosphine Osmium Polyhydrides: Hydrogen Delocalization in [OsH₅P₃]⁺ Systems

Synthesis and Characterization of Mixed-Phosphine Osmium Polyhydrides: Hydrogen Delocalization in [OsH₅P₃]⁺ Systems

One-Pot Synthesis of Metal Primary Phosphine Complexes from OPCl₂R or PCl₂R. Isolation and Characterization of Primary Alkylphosphine Complexes of a Metalloporphyrin

Electrophilic Aromatic Substitution Reactions of a Tungsten-Coordinated Phosphirenyl Triflate

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PH‐Functionalized Phosphenium Complexes [C5R5(OC)2 WP(H)R′] (R′ = tBu, sMes): Synthesis, Isomerization, and Transformation into Hydrido Complexes Containing a tBuP(H)OH Ligand

Cited by 21 publications

References 17 publications

Synthesis and Characterization of Mixed-Phosphine Osmium Polyhydrides: Hydrogen Delocalization in [OsH5P3]+ Systems

Synthesis and Characterization of Mixed-Phosphine Osmium Polyhydrides: Hydrogen Delocalization in [OsH5P3]+ Systems

One-Pot Synthesis of Metal Primary Phosphine Complexes from OPCl2R or PCl2R. Isolation and Characterization of Primary Alkylphosphine Complexes of a Metalloporphyrin

Electrophilic Aromatic Substitution Reactions of a Tungsten-Coordinated Phosphirenyl Triflate

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PH‐Functionalized Phosphenium Complexes [C₅R₅(OC)₂ WP(H)R′] (R′ = tBu, sMes): Synthesis, Isomerization, and Transformation into Hydrido Complexes Containing a tBuP(H)OH Ligand

Synthesis and Characterization of Mixed-Phosphine Osmium Polyhydrides: Hydrogen Delocalization in [OsH₅P₃]⁺ Systems

Synthesis and Characterization of Mixed-Phosphine Osmium Polyhydrides: Hydrogen Delocalization in [OsH₅P₃]⁺ Systems

One-Pot Synthesis of Metal Primary Phosphine Complexes from OPCl₂R or PCl₂R. Isolation and Characterization of Primary Alkylphosphine Complexes of a Metalloporphyrin