Reinvestigations of some reactions of metal carbonyl anions with cyclopropenium cations. Conversion of .eta.3-cyclopropenyl to .eta.3-cyclobutenonyl ligands

Hughes, Russell P.; Lambert, J.M.; Reisch, J; Smith, William

doi:10.1021/om00070a027

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“…Comparisons of metal-C5 and metal-C3 centroid distances in other crystallographically characterized ?/3-cyclopropenyl (29) See note at end of text regarding supplementary material. 2) 39 (1)°C (21) 4319 ( 3) 8981 (1) 1643 (1) 63 (2)" C (22) 4779 ( 3) 9722 (1) 1343 (1) 75 (2)°C (23) 5543 ( 3) 10246 (1) 1982 (1) 67 (2)°C (24) 5846 (3) 10030 (1) 2922 (1) 62 (2)" C (25) 5389 (3) 9290 (1) 3223 (1) 48 (1)= C (26) 4624 ( 3) 8765 (1) 2584 ( 1) 38 (1)°C (31) 80 (7) 7516 ( 3) 2357 ( 5) 54 ( 4)°C (32) -1284 (7) 7829 (3) 2133 ( 5) 76 ( 5)°C (33) -1531 (7) 8646 (3) 2272 ( 5) 82 ( 6)" C(34) -414 (7) 9150 (3) 2636 ( 5) 76 (5)" C(35) 950 ( 7) 8837 (3) 2861 ( 5) 52 ( 4)°C (36) 1197 (7) 8020 ( 3) 2721 ( 5) 39 (3)" 0 Equivalent isotropic U defined as one-third of the trace of the orthogonalized U¡j tensor. compounds are provided in Table V.…”

Section: Discussionmentioning

confidence: 99%

Oxidative addition of cyclopropenyl cations to zerovalent molybdenum and tungsten centers. Synthesis of .eta.3-cyclopropenyl and .eta.3-oxocyclobutenyl complexes of molybdenum(II) and tungsten(II). Crystal and molecular structures of [Mo(.eta.5-C5H5)(.eta.3-C3Ph2R)(CO)2] (R = Ph, tert-Bu)

Hughes¹,

Reisch²,

Rheingold³

1985

Organometallics

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Oxidative addition of triphenylcyclopropenyl hexafluorophosphate to [Mo(CO)3(MeCN)3] affords the cationic cyclopropenyl complex [Mo(j7-C3Ph3)(CO)2(MeCN)3]+[PF6"], 8, which reacts with cyclopentadienylthallium to give excellent yields of the neutral rf-cvclopropenyl complex [Mo(r)-C3Ph:!)(jj-C5H5)(CO)2], 6a. Similar one-pot syntheses of the analogous complexes [M(7j-C3Ph2-t-Bu)(j)-C5H5)(CO)2] (6b, = Mo; 6c, M = W) from the tert-butyldiphenylcyclopropenyl cation are described. In contrast, use of triphenylcyclopropenyl chloride or bromide in the reaction with [M(CO)3(MeCN)3] (M = Mo, W) affords ultimately the ring-expanded oxocyclobutenyl compounds 9, presumably via intermediates 10. Thermal reaction of the (triphenylcyclopropenyl)molybdenum complex 6a with PMe2Ph or P(OPh)3 results in ring expansion to give the oxocyclobutenyl complexes 11. The dynamic behavior of the cyclopropenyl ligands in compounds 6 is reported, and compounds 6a and 6b have been characterized by single-crystal X-ray diffraction studies: 6a crystallizes in the monoclinic space group P2x/n with a = 9.545 (2) Á, b = 16.580 (3) Á, c = 14.463 (3) Á, ß = 98.47 (2)°, and Z -4; 6b crystallizes in the monoclinic space group P21/c with a = 8.488 (2) A, b = 16.394 (4) A; c = 16.168 (4) A, ß = 95.28 (2)°, and Z = 4. Both compounds clearly contain tj3-cyclopropenyl ligands, and their structures are compared and contrasted with those of other cyclopropenyl and metallacyclobutadiene complexes.

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Section: Discussionmentioning

confidence: 99%

Oxidative addition of cyclopropenyl cations to zerovalent molybdenum and tungsten centers. Synthesis of .eta.3-cyclopropenyl and .eta.3-oxocyclobutenyl complexes of molybdenum(II) and tungsten(II). Crystal and molecular structures of [Mo(.eta.5-C5H5)(.eta.3-C3Ph2R)(CO)2] (R = Ph, tert-Bu)

Hughes¹,

Reisch²,

Rheingold³

1985

Organometallics

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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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η ³ ‐Cyclopropenyl‐ und η ³ ‐Oxocyclobutenyl‐Eisen‐Komplexe. Die Kristallstrukturen von (η ³ ‐C ₃ Ph ₃ )Fe(CO) ₂ NO und (η ³ ‐C ₃ Ph ₃ CO)Fe(CO) ₂ NO

1983

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Bei der Umsetzung von 1,2,3-Triphenylcyclopropenylium-brornid rnit Natrium-tricarbonylnitrosylferrat( -I) in Methanol erhielt Coffey 1962l) in kleinen Ausbeuten eine rotbraune Verbindung. Hierfiir wurden Struktur 1 den Vorzug erhielt.Eine Kurzmitteilung uber eine erneute Untersuchung'' dieser Reaktion veranlal3t uns, unsere eigenen Ergebnisse mitzuteilen.Bei der Umsetzung von [C3Ph3]C1 mit Na [Fe(CO),NO] in THF (20°C) fanden wir vier Produkte (2a, 3, 4, 5), die sich chromatographisch gut trennen liel3en.Die Verbindung 3 ist nach ihren physikalischen und IR-spektroskopischen Daten identisch mit der Coffeyschen Verbindung und konnte von uns u. a. durch eine Ront-0

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Reinvestigations of some reactions of metal carbonyl anions with cyclopropenium cations. Conversion of .eta.3-cyclopropenyl to .eta.3-cyclobutenonyl ligands

Cited by 15 publications

References 0 publications

Oxidative addition of cyclopropenyl cations to zerovalent molybdenum and tungsten centers. Synthesis of .eta.3-cyclopropenyl and .eta.3-oxocyclobutenyl complexes of molybdenum(II) and tungsten(II). Crystal and molecular structures of [Mo(.eta.5-C5H5)(.eta.3-C3Ph2R)(CO)2] (R = Ph, tert-Bu)

Oxidative addition of cyclopropenyl cations to zerovalent molybdenum and tungsten centers. Synthesis of .eta.3-cyclopropenyl and .eta.3-oxocyclobutenyl complexes of molybdenum(II) and tungsten(II). Crystal and molecular structures of [Mo(.eta.5-C5H5)(.eta.3-C3Ph2R)(CO)2] (R = Ph, tert-Bu)

Chemistry of Metallacyclobutadienes

η ³ ‐Cyclopropenyl‐ und η ³ ‐Oxocyclobutenyl‐Eisen‐Komplexe. Die Kristallstrukturen von (η ³ ‐C ₃ Ph ₃ )Fe(CO) ₂ NO und (η ³ ‐C ₃ Ph ₃ CO)Fe(CO) ₂ NO

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Reinvestigations of some reactions of metal carbonyl anions with cyclopropenium cations. Conversion of .eta.3-cyclopropenyl to .eta.3-cyclobutenonyl ligands

Cited by 15 publications

References 0 publications

Oxidative addition of cyclopropenyl cations to zerovalent molybdenum and tungsten centers. Synthesis of .eta.3-cyclopropenyl and .eta.3-oxocyclobutenyl complexes of molybdenum(II) and tungsten(II). Crystal and molecular structures of [Mo(.eta.5-C5H5)(.eta.3-C3Ph2R)(CO)2] (R = Ph, tert-Bu)

Oxidative addition of cyclopropenyl cations to zerovalent molybdenum and tungsten centers. Synthesis of .eta.3-cyclopropenyl and .eta.3-oxocyclobutenyl complexes of molybdenum(II) and tungsten(II). Crystal and molecular structures of [Mo(.eta.5-C5H5)(.eta.3-C3Ph2R)(CO)2] (R = Ph, tert-Bu)

Chemistry of Metallacyclobutadienes

η 3 ‐Cyclopropenyl‐ und η 3 ‐Oxocyclobutenyl‐Eisen‐Komplexe. Die Kristallstrukturen von (η 3 ‐C 3 Ph 3 )Fe(CO) 2 NO und (η 3 ‐C 3 Ph 3 CO)Fe(CO) 2 NO

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η ³ ‐Cyclopropenyl‐ und η ³ ‐Oxocyclobutenyl‐Eisen‐Komplexe. Die Kristallstrukturen von (η ³ ‐C ₃ Ph ₃ )Fe(CO) ₂ NO und (η ³ ‐C ₃ Ph ₃ CO)Fe(CO) ₂ NO