Molybdenum-based alkyne–isocyanide coupling reactions: synthesis of a reactive diiminometallacyclopentene complex

Adams, Christopher J.; Anderson, Kirsty M.; Bartlett, Ian M.; Connelly, Neil G.; Orpen, A. Guy; Paget, Timothy J.; Phetmung, Hirihattaya; Smith, David W.

doi:10.1039/b010018h

Cited by 26 publications

(15 citation statements)

References 18 publications

(18 reference statements)

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“…For example, [FeF(dppe)(h-C 5 Me 5 )][PF 6 ] is formed in the oxidation of [Fe(dppe)(h-C 5 Me 5 )][ PF 6 ] with [Fe(h-C 5 H 5 ) 2 ][PF 6 ], 5 and [MoF(CNxylyl) 4 (h-C 5 Me 5 )][BF 4 ] 2 results from the reaction of Ag [BF 4 ] with [Mo(CNxylyl) 4 (h-C 5 Me 5 )][ BF 4 ]. 6 A more rational synthesis of [WF 2 (h-PhC∫CPh)Tp¢] + was then developed using N-fluoropyridinium tetrafluoroborate, [Fpy][BF 4 ], as both the strong oxidant and a potential source of the second fluoride ligand. Thus, treatment of [WF(CO)(h-PhC∫CPh)Tp¢] with [Fpy][BF 4 ] in CH 2 Cl 2 led to slow loss of the IR carbonyl band and formation of a red-orange solution which was filtered through Celite and then evaporated to dryness in vacuo.…”

Section: Resultsmentioning

confidence: 99%

“…The discovery of the one-electron oxidation of [Cr(CO) 2 (h-RC∫CR)(h 6 -arene)] and the one-electron reduction of [M(CO) 2 (h-RC∫CR)Tp¢] + , and the consequent structural characterisation of the redox pairs [Cr(CO) 2 (h-PhC∫CPh)(h 6 -C 6 Me 5 H)] z (z = 0, d 6 and 1+, d 5 ) 1 and [Mo(CO) 2 (h-PhC∫CPh)Tp¢] z (z = 0, d 5 and 1+, d 4 ), 2 enabled us to show that stepwise electron removal from a (formally) d 6 complex converted the coordinated alkyne from a two-to a three-to a four-electron donor. Halide substitution of one carbonyl ligand of [M(CO) 2 (h-RC∫CR)Tp¢] + then gave [MX(CO)(h-RC∫CR)Tp¢] (M = Mo or W, X = halide) which was oxidised to the isolable d 3 cation [MX(CO)(h-RC∫CR)Tp¢] + , again structurally characterised (M = W, X = Cl or Br).…”

Section: Introductionmentioning

confidence: 99%

“…This paper describes the full characterisation of [MX 1 X 2 (h-RC∫CR)Tp¢] + (R = Me, M = W, X 1 = X 2 = F; R = Ph, M = Mo, X 1 = X 2 = F; M = W, X 1 = X 2 = F or Cl; X 1 = F, X 2 = Cl) and the one-electron reduction to the neutral analogues [MX 1 X 2 (h-RC∫CR)Tp¢], completing a redox family tree in which well defined d 6 and d 2 alkyne complexes are formally connected by a series of ligand substitution and one-electron transfer reactions.…”

Section: Introductionmentioning

confidence: 99%

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The d³/d²alkyne complexes [MX₂(η-RCCR)Tp′]^z(X = halide, z = 0 and 1+): final links in a d⁶–d²redox family tree

et al. 2009

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The d4 halide complexes [MX(CO)(eta-RC[triple bond, length as m-dash]CR)Tp'] [R = Me, M = W, X = F; R = Ph, M = Mo or W, X = F or Cl; Tp' = hydrotris(3,5-dimethylpyrazolyl)borate] undergo two-electron oxidation in the presence of a halide source to give the d2 monocations [MX1X2(eta-PhC[triple bond, length as m-dash]CPh)Tp']+ (R = Me, M = W, X1 = X2 = F; R = Ph, M = Mo, X1 = X2 = F or Cl; M = W, X1 = X2 = F or Cl; X1 = F, X2 = Cl). Each monocation (R = Ph) shows two reversible one-electron reductions (the second process was not detected for R = Me) corresponding to the stepwise formation of the neutral d3 and monoanionic d4 analogues, [MX1X2(eta-PhC[triple bond, length as m-dash]CPh)Tp'] and [MX1X2(eta-PhC[triple bond, length as m-dash]CPh)Tp']- respectively; the potentials for the two processes can be 'tuned' over a range of ca. 1.0 V by varying M and X. Chemical one-electron reduction of [MX2(eta-PhC[triple bond, length as m-dash]CPh)Tp']+ gave [MX2(eta-PhC[triple bond, length as m-dash]CPh)Tp'] (M = Mo or W, X = F or Cl). X-Ray structural studies on the redox pairs [WX2(eta-PhC[triple bond, length as m-dash]CPh)Tp']z (X = F and Cl, z = 0 and 1+) show the alkyne to bisect the X-W-X angle in the d2 cations but align more closely with one M-X bond in the neutral d3 molecules, consistent with the anisotropic ESR spectra of the latter; the solution ESR spectrum of [MoF2(eta-PhC[triple bond, length as m-dash]CPh)Tp'] showed equivalent fluorine atoms, i.e the alkyne oscillates at room temperature. The successful isolation of [MX2(eta-PhC[triple bond, length as m-dash]CPh)Tp']+ and [MX2(eta-PhC[triple bond, length as m-dash]CPh)Tp'] completes a series in which d6 to d2 alkyne complexes are linked in a redox family tree by sequential one-electron transfer and substitution reactions. The implications for such trees in the production of new species and the selective synthesis of paramagnetic complexes acting as synthetically useful 'alkyne radicals' are discussed.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The d³/d²alkyne complexes [MX₂(η-RCCR)Tp′]^z(X = halide, z = 0 and 1+): final links in a d⁶–d²redox family tree

et al. 2009

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“…Class B MCBDs display weaker π bonding between the metal and the C α atoms, and no interaction between the metal and the C β atom 8c,d. These MBCDs contain mostly a six‐coordinate metal center in a lower oxidation state 3a. 4–7 Remarkably, MCBDs are either planar or puckered metallacycles, which may display extensive or only little π‐electron delocalization.…”

Section: Methodsmentioning

confidence: 99%

Photochemistry of a Puckered Ferracyclobutadiene in Liquid Solution Studied by Time‐Resolved Fourier‐Transform Infrared Spectroscopy

Torres-Alacan

Das

Wezisla

et al. 2015

Chemistry A European J

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Flash photolysis combined with step-scan and rapid-scan Fourier-transform infrared spectroscopy was carried out to explore the photochemistry of a puckered, quasi-square pyramidal ferracyclobutadiene, [Fe{κ(2) -C3 (NEt2 )3 }(CO)3 ]BF4 ([1]BF4 ), that features three additional carbonyl ligands in the metal coordination sphere. In liquid solution at room temperature, an excitation with λ=355 nm light resulted in the loss of one CO ligand, which is cleaved from a basal metal-coordination site. Within the time resolution of the experiment, a solvent molecule promptly refills the resultant vacancy at the coordinatively unsaturated metal center. In the weakly interacting liquid, dichloromethane, the counterion of the complex is subsequently able to substitute the solvent in the coordination sphere of the iron center, thereby forming as a stable product a neutral dicarbonyl tetrafluoroborato iron(0) species containing a four-membered ferracycle.

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“…Similarly, treatment of ferracyclobutinimine 24 with Et 3 OBF 4 produced ferracyclobutadiene 25 . In a related transformation, treatment of the diiminomolybdenacyclopentene 26 with HBF 4 produced the molybdenacyclobutadiene 27 . The reaction may proceed by initial protonation of an imine nitrogen of the diiminometallacyclopentene complex followed by a deinsertion of xylyl isocyanide.…”

Section: Synthetic Routes To Construct Metallacyclobutadiene Ringsmentioning

confidence: 99%

Chemistry of Metallacyclobutadienes

Cui

Lin

Jia

2018

Chemistry An Asian Journal

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Metallacyclobutadienes are analogues of cyclobutadienes in which one of the cyclobutadiene CR groups has been formally replaced by a transition-metal fragment. These metallacycles are interesting because they can play an important role in catalysis and can serve as starting materials for the syntheses of organometallic compounds such as metallabenzene, η -cyclopentadienyl, and η -cyclopropenyl complexes. Unlike cyclobutadienes, metallacyclobutadienes can be significantly more stable. A number of metallacyclobutadienes have now been isolated and thoroughly characterized, especially for those that contain transition metals of groups 5-9. Their properties have also been actively investigated. This article highlights the chemistry of metallacyclobutadienes with reference to their syntheses, reactivity, and structural properties.

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Molybdenum-based alkyne–isocyanide coupling reactions: synthesis of a reactive diiminometallacyclopentene complex

Cited by 26 publications

References 18 publications

The d³/d²alkyne complexes [MX₂(η-RCCR)Tp′]^z(X = halide, z = 0 and 1+): final links in a d⁶–d²redox family tree

The d³/d²alkyne complexes [MX₂(η-RCCR)Tp′]^z(X = halide, z = 0 and 1+): final links in a d⁶–d²redox family tree

Photochemistry of a Puckered Ferracyclobutadiene in Liquid Solution Studied by Time‐Resolved Fourier‐Transform Infrared Spectroscopy

Chemistry of Metallacyclobutadienes

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Molybdenum-based alkyne–isocyanide coupling reactions: synthesis of a reactive diiminometallacyclopentene complex

Cited by 26 publications

References 18 publications

The d3/d2alkyne complexes [MX2(η-RCCR)Tp′]z(X = halide, z = 0 and 1+): final links in a d6–d2redox family tree

The d3/d2alkyne complexes [MX2(η-RCCR)Tp′]z(X = halide, z = 0 and 1+): final links in a d6–d2redox family tree

Photochemistry of a Puckered Ferracyclobutadiene in Liquid Solution Studied by Time‐Resolved Fourier‐Transform Infrared Spectroscopy

Chemistry of Metallacyclobutadienes

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The d³/d²alkyne complexes [MX₂(η-RCCR)Tp′]^z(X = halide, z = 0 and 1+): final links in a d⁶–d²redox family tree

The d³/d²alkyne complexes [MX₂(η-RCCR)Tp′]^z(X = halide, z = 0 and 1+): final links in a d⁶–d²redox family tree