Synthesis and chemistry of chiral rhenium acyls (.eta.-C5H5)Re(NO)(PPh3)(COR)

Buhro, William E.; Wong, A.; Merrifield, James H.; Lin, Gong Yu; Constable, Anthony C.; Gladysz, J. A.

doi:10.1021/om50006a026

Cited by 48 publications

(30 citation statements)

References 9 publications

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“…A very limited number of similar reactions and compounds have been reported previously. The formation of Fischer‐type carbenes of the composition [Re(NO)(Cp)(PPh 3 ){C(OMe)R}] (R=Me, Ph) has been observed during reactions of acyl complexes with MeSO 3 F, [49] and also some analogous manganese complexes are known [50] . Additionally, there exist two related platinum compounds, which are formed from H 2 PtCl 6 , when it is treated with Me 3 SiCH 2 C≡CH or Me 3 SiC≡CH in iso‐propanol [51,52] …”

Section: Resultsmentioning

confidence: 99%

[Tc(NO)Cl(Cp)(PPh₃)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

2021

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Reactions of the chiral organometallic technetium(I) compound [Tc(NO)Cl(Cp)(PPh3)] (1 a) with phosphines and alkynes give unexpected products such as the dimeric cation [{Tc(NO)(Cp)(PPh3)}2Cl]+ (4) or the Fischer‐type carbene [Tc(NO)(Cp)(PPh3){C(OR)C2H4PPh3}]2+ (5). Both products could be isolated as PF6− salts and studied by spectroscopic methods and X‐ray diffraction. While [Tc(NO)(Cp)(PMe3)(PPh3)](PF6) (2PF6) can be obtained from 1 a, PMe3 and Ag(PF6) under ambient conditions, the synthesis of the corresponding bis‐triphenylphosphine complex [Tc(NO)(Cp)(PPh3)2](PF6) (3PF6) requires high temperatures and long reaction times. The products are stable in air.

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Section: Resultsmentioning

confidence: 99%

[Tc(NO)Cl(Cp)(PPh₃)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

2021

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“…The sample also contained small amounts ( < 5%) of other unidentified isomers of 6c (detected using GC-MS). Compound (12), 128 (20), 115 (30), 102 (6), 91 (80) and 77 (26%).…”

Section: Methodsmentioning

confidence: 99%

Synthesis and reactions of acyl(cyclohexadienyl)manganates

Sheridan¹,

Padda²,

Chaffee³

et al. 1992

J. Chem. Soc., Dalton Trans.

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The cyclohexadienyl complexes [Mn(q5-C,H,R1)(CO),] 1 (R' = exo-H, M e or C,H,Me-4) react with LiR2 (R2 = M e or Ph) to give acylmetalates [Li(OEt,)] [Mn(7\5-C,H,R1)(CO),{C(0)R2}] 2. Complex 2 ( R1 = Me, R2 = Ph) has been characterised by an X-ray crystallographic study: orthorhombic, space group P212121, a = 9.1 13(2), b = 14.491 (8), c = 32.803(9) A, R = 0.064 for 1 4 5 8 independent reflections. Protonation of 2 with HBF,*Et20 induces an aryl-or alkyl-group transfer t o the endo face of the cyclohexadienyl ring yielding t h e new agostic cyclohexenyl complexes [Mn(q3:CHC6H,R1R2) (CO),] 3. The cyclohexenyl ligands can be decomplexed from the metal via treatment of 3 with 1,2-bis-(dipheny1phosphino)ethane (dppe) in tetrahydrofuran to afford mixtures of substituted cyclohexa-l,3dienes and [MnH(CO),(dppe)]. The acylmetalates 2 react with [NO] [BF,] at -78 "C to give [Mn(q5-C,H,R1) (CO) (NO){C(O) R2}] which decompose at room temperature to form the trans-disubstituted acylcyclohexadienes C,H,R1[C(0)R2]. Reaction of 2 with electrophiles SiMe,CI, [Me,O] [BF,] or [Et,O] [BF,] results in 0 alkylation and formation of stable carbene complexes [Mn(q5-C6H,R1)(CO),-{C(OE)R2}] ( E = SiMe,, M e or Et).

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“…Thus, 3 is one o f three optically active [(^5-C5H 5)Re(NO)(PPh3)(X)]"+ complexes found to date (out of over one hundred) with an anom alous sign o f [a]589. The others are the benzoyl complex (7 5-C5H 5)Re(NO)(PPh3)(COC6H 5) and the phenylacetylene complex [(^5-C5H 5)Re(NO)(PPh3)-(H C = C P h )]+BF4~ [17].…”

Section: Syntheses O F Optically Active Complexesmentioning

confidence: 99%

Synthesis and Structure of σ-Complexes of the Chiral Rhenium Lewis Acid [(η⁵-C₅H₅)Re(NO)(PPh₃)]⁺ and Aromatic Nitrogen Heterocycles

Dewey

Knight

Arif

et al. 1992

Zeitschrift Für Naturforschung B

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Synthesis and chemistry of chiral rhenium acyls (.eta.-C5H5)Re(NO)(PPh3)(COR)

Cited by 48 publications

References 9 publications

[Tc(NO)Cl(Cp)(PPh₃)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

[Tc(NO)Cl(Cp)(PPh₃)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

Synthesis and reactions of acyl(cyclohexadienyl)manganates

Synthesis and Structure of σ-Complexes of the Chiral Rhenium Lewis Acid [(η⁵-C₅H₅)Re(NO)(PPh₃)]⁺ and Aromatic Nitrogen Heterocycles

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Synthesis and chemistry of chiral rhenium acyls (.eta.-C5H5)Re(NO)(PPh3)(COR)

Cited by 48 publications

References 9 publications

[Tc(NO)Cl(Cp)(PPh3)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

[Tc(NO)Cl(Cp)(PPh3)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

Synthesis and reactions of acyl(cyclohexadienyl)manganates

Synthesis and Structure of σ-Complexes of the Chiral Rhenium Lewis Acid [(η5-C5H5)Re(NO)(PPh3)]+ and Aromatic Nitrogen Heterocycles

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Product

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[Tc(NO)Cl(Cp)(PPh₃)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

[Tc(NO)Cl(Cp)(PPh₃)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

Synthesis and Structure of σ-Complexes of the Chiral Rhenium Lewis Acid [(η⁵-C₅H₅)Re(NO)(PPh₃)]⁺ and Aromatic Nitrogen Heterocycles