Synthesis and reactivity of η<sup>2</sup>(4e)-alkyne and η<sup>2</sup>(3e)-vinyl complexes of rhenium

Carfagna, Carla; Carr, N.; Deeth, Robert J.; Dossett, Stephen J.; Green, Michael; Mahon, Mary F.; Vaughan, C. Wheaton

doi:10.1039/dt9960000415

Cited by 33 publications

(26 citation statements)

References 25 publications

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“…Pombeiro isolated trans -(Ph 2 PCH 2 CH 2 PPh 2 ) 2 ClRe[η 2 -C(CH 2 Ph)CH 2 ) + BF 4 - from the protonation of the allene complex trans -(Ph 2 PCH 2 CH 2 PPh 2 ) 2 ClRe(η 2 -CHPh=CCH 2 ) with HBF 4. Green prepared the neutral 1-metallacyclopropene C 5 H 5 (PPh 3 )BrRe(η 2 -CPhCHPh) by hydride addition to the 4-electron donor alkyne complex C 5 H 5 (PPh 3 )BrRe(η 2 -PhC⋮CPh) + PF 6 - …”

Section: Introductionmentioning

confidence: 99%

Protonation of Rhenium Alkyne Complexes Produces η³-Allyl Rhenium Complexes via Observable 1-Metallacyclopropene Intermediates

et al. 1998

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Protonation of the rhenium η 2 -alkyne complex C 5 Me 5 (CO) 2 Re(η 2 -MeCtCMe) (4) with HBF 4 at room temperature produced the η 3 -allyl complex C 5 Me 5 (CO) 2 Re(η 3 -exo,anti-MeHC-CH-CH 2 ) + BF 4 -(5). The protonation of 4 at -78 °C occurred at rhenium to give the rhenium alkyne hydride complex C 5 Me 5 (CO) 2 -ReH(η 2 -MeCtCMe) + BF 4 -(6). At -16 °C, net proton migration from rhenium to the alkyne ligand of 6 occurred to produce the 1-metallacyclopropene complex C 5 Me 5 (CO) 2 Re(η 2 -CMeCHMe) + BF 4 -(7), which then rearranged to form the η 3 -allyl complex 5. The degenerate rearrangement of 7 by hydride migration between the two metallacyclopropene carbons was demonstrated by deuterium labeling. Protonation of the rhenium η 2 -alkyne complex C 5 Me 5 (CO) 2 Re(η 2 -PhCtCPh) (10) with HBF 4 at -78 °C initially produced the rhenium alkyne hydride complex C 5 Me 5 (CO) 2 ReH(η 2 -PhCtCPh) + BF 4 -(11), which was observed spectroscopically. Upon warming to room temperature, 11 was converted to the stable 1-metallacyclopropene complex C 5 Me 5 (CO) 2 -Re(η 2 -CPhCHPh) + BF 4 -(12), which was characterized by X-ray crystallography. Hybrid density functional theory calculations and natural bond orbital analysis were performed on the 1-metallacyclopropene cation [C 5 H 5 (CO) 2 Re(η 2 -MeCCHMe)] + to compare η 2 -vinyl vs 1-metallacyclopropene formulations.

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Section: Introductionmentioning

confidence: 99%

Protonation of Rhenium Alkyne Complexes Produces η³-Allyl Rhenium Complexes via Observable 1-Metallacyclopropene Intermediates

et al. 1998

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“…Adapting a procedure described by Green, [9] the reaction of [(η 5 -C 5 H 5 )Re(CO) 2 Br 2 ] with bis(benzylthio)acetylene (1) at elevated temperature leads to the formation of the η 2 -alkyne complex [(η 5 -C 5 H 5 )Re(1)Br 2 ] (2) in good yield. The intense green, air-stable complex 2 was characterized by a 13 C NMR resonance at δ = 207.5 ppm, which is consistent with a side-on four-electron donor alkyne complex.…”

Section: Resultsmentioning

confidence: 99%

“…In general, the structure is similar to related Re III alkyne complexes. [9,10] The C1-C2 vector lies parallel to one of the rhenium bromide bonds leading to signifi- Further reaction of complex 2 with an excess of alkyne 1 in refluxing toluene led to the formation of a new red compound 3, which was isolated in analytically pure form by crystallization. Mass spectrometry indicated 3 to be an addition product of 1 and 2, while the NMR spectroscopic data of 3 appeared hard to elucidate.…”

Section: Resultsmentioning

confidence: 99%

Facile Formation of a Rhenium Allenylcarbene Complex with an Internal Dithioalkyne

et al. 2010

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The η 2 -alkyne complex [(η 5 -C 5 H 5 )Re(1)Br 2 ], 2, (1 = BnSC 2 SBn) reacts with an excess of the dithioalkyne 1 to give the addition product [(η 5 -C 5 H 5 )ReBr 2 {η 3 -(BnS) 2 C 2 C(SBn)-C(SBn)}], 3, displaying a ReC 3 ring with an exocyclic double bond. The molecular structures of the complexes 2 and 3 were determined by single-crystal X-ray diffraction. The nonplanarity of the ReC 3 ring and the largely equal C-C bond lengths within the ring reveal 3 to be a resonance hybrid of an allenylcarbene complex and a folded rhenacyclobutene system. DFT calculations show that complex type 3 is

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“…The outcome of the reaction of [(η 5 ‐C 5 H 5 )Re(CO) 2 X 2 ], ( X = Br, I), with tolane or the related sulfide derivative C 2 (SBn) 2 can partially be controlled by stoichiometry and reaction time. The alkyne complexes 1a , 2a (Scheme ), and [(η 5 ‐C 5 H 5 )Re{C 2 (SBn) 2 )I 2 ] ( 2b ) are the main products, if the alkynes were applied in moderate excess with short reaction times. Herein, the iodido derivative 2b was isolated and fully characterized.…”

Section: Resultsmentioning

confidence: 99%

Square Planar Coordination of Silver in a η⁴‐Cyclobutadiene‐(η⁵‐C₅H₅)ReBr₂ Complex Framework

Kleinschmidt

Hinz

Villinger

et al. 2018

Zeitschrift anorg allge chemie

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Halide addition and abstraction experiments with the cationic rhenacyclopentatriene [(η5‐C5H5){ReC4(SBn)4}Br]BF4 and the side‐on cyclobutadiene complexes [(η5‐C5H5)(η4‐C4Ph4)ReX2] (X = Br, I), respectively, are described. Reversible interconversion of both coordination modes of the metal bonded C4R4 moiety depending on the presence or absence of the second bromide ligand is demonstrated for the sulfide derivative. However, formation of the [(η5‐C5H5)(ReC4Ph4)X]+ congener by halide abstraction at [(η5‐C5H5)(η4‐C4Ph4)ReX2] turned out to be impossible. Instead, formation of silver halide complexes with the halide bridging rhenium and silver under retention of the metalorganic scaffold are observed. Governed by the phenyl substituent framework a square‐planar coordination environment about the Ag cation is adopted for X = Br. Changing X = Br by X = I led to the formation of a heptanuclear complex with di‐ and three‐coordinate silver ions.

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Synthesis and reactivity of η²(4e)-alkyne and η²(3e)-vinyl complexes of rhenium

Cited by 33 publications

References 25 publications

Protonation of Rhenium Alkyne Complexes Produces η³-Allyl Rhenium Complexes via Observable 1-Metallacyclopropene Intermediates

Protonation of Rhenium Alkyne Complexes Produces η³-Allyl Rhenium Complexes via Observable 1-Metallacyclopropene Intermediates

Facile Formation of a Rhenium Allenylcarbene Complex with an Internal Dithioalkyne

Square Planar Coordination of Silver in a η⁴‐Cyclobutadiene‐(η⁵‐C₅H₅)ReBr₂ Complex Framework

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Synthesis and reactivity of η2(4e)-alkyne and η2(3e)-vinyl complexes of rhenium

Cited by 33 publications

References 25 publications

Protonation of Rhenium Alkyne Complexes Produces η3-Allyl Rhenium Complexes via Observable 1-Metallacyclopropene Intermediates

Protonation of Rhenium Alkyne Complexes Produces η3-Allyl Rhenium Complexes via Observable 1-Metallacyclopropene Intermediates

Facile Formation of a Rhenium Allenylcarbene Complex with an Internal Dithioalkyne

Square Planar Coordination of Silver in a η4‐Cyclobutadiene‐(η5‐C5H5)ReBr2 Complex Framework

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Synthesis and reactivity of η²(4e)-alkyne and η²(3e)-vinyl complexes of rhenium

Protonation of Rhenium Alkyne Complexes Produces η³-Allyl Rhenium Complexes via Observable 1-Metallacyclopropene Intermediates

Protonation of Rhenium Alkyne Complexes Produces η³-Allyl Rhenium Complexes via Observable 1-Metallacyclopropene Intermediates

Square Planar Coordination of Silver in a η⁴‐Cyclobutadiene‐(η⁵‐C₅H₅)ReBr₂ Complex Framework