Reaktion von Acetyl‐Übergangsmetallkomplexen mit Phosphor‐Yliden – ein weiteres Beispiel zur Halogenid/Metallat‐Analogie

Malisch, Wolfgang; Blau, Herbert; Haaf, Franz

doi:10.1002/cber.19811140905

Cited by 21 publications

(4 citation statements)

References 55 publications

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“…Previous attempts to deprotonate the acetyl ligand of [Mo(COMe)(CO) 2 (PPh 3 )(η-C 5 H 5 )] with LiBu n or the Wittig reagent PPh 3 ᎐ ᎐ CH 2 resulted only in loss of the acyl ligand and formation of the [Mo(CO) 2 (PPh 3 )(η-C 5 H 5 )] Ϫ anion. 8, 9 In contrast to [Fe(COMe)(CO)(PPh 2 H)(η-C 5 H 5 )], which can be successfully deprotonated with either of these reagents, their use in the current reaction led to mixtures of products arising from competing phosphine deprotonation and acyl loss in both cases.…”

Section: Low-temperature Deprotonation-alkylation Reactionsmentioning

confidence: 93%

Synthesis of acylphosphine complexes by controllable migration of acyl groups from molybdenum to phosphido ligands †

Adams¹,

Bailey²,

Blenkiron³

et al. 1997

J. Chem. Soc., Dalton Trans.

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Section: Low-temperature Deprotonation-alkylation Reactionsmentioning

confidence: 93%

Synthesis of acylphosphine complexes by controllable migration of acyl groups from molybdenum to phosphido ligands †

Adams¹,

Bailey²,

Blenkiron³

et al. 1997

J. Chem. Soc., Dalton Trans.

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“…492 Deprotonation o f [Mo(COR 1 )(CO) 2 (PPh 2 H)Cp] at low temperature occurs at the phosphine, producing [Mo(COR')(CO) 2 (PPh 2 R 2 )Cp] on alkylation with R 2 I (R 1 , R 2 = Me, Et); i f the same reaction is carried out at room temperature, migration of the acyl group to phosphorus occurs to yield [Mo(R 2 )(CO) 2 (PPh 2 COR' )Cp] . 71 …”

Section: ' 425 Functionalization Of the Cp R I N G In [Wme(co) 3 Cp] mentioning

confidence: 97%

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Morris

1995

Comprehensive Organometallic Chemistry II

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“…The latter reagent, however, yields the diacetyl derivative as well. The products are unstable and decompose with the production of phosphane oxides 19. The lack of applications and stability notwithstanding, we have explored the oxidative formation of 1‐tributylphosphoranylidene‐2‐propanones by treating acetone with the corresponding phosphane, Bu 3 P. The same blue to purple color change, as observed in the reaction with Ph 3 P, occurs in the visible region.…”

mentioning

confidence: 96%

“…Aliphatic, electron‐rich, 1‐trialkylphosphoranylidene‐2‐propanones, on the other hand, are not used extensively 18. Indeed, only the methyl, ethyl, and butyl derivatives are reported 19. Their preparation can be accomplished by the stoichiometric acetylation of phosphorus ylides, R 3 P=CH 2 , with an acetyl metal complex, or acetyl chloride.…”

mentioning

confidence: 99%

Synthesis and Structure of a Biconcave Cobalt Perfluorophthalocyanine and Its Catalysis of Novel Oxidative Carbon-Phosphorus Bonds Formation by Using Air

et al. 2002

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One of the major challenges of modern chemistry, homogeneous aerobic oxidations, poses the additional challenge of designing suitable catalysts that are not only active, but resist self-oxidation as well. For transition metal complexes, this of 3, a dose of 5 mmol kg À1 induced 60 % regression. [18] These results suggest that the introduction of bulky perfluoroalkyl groups results in higher tumor regression at lower photosensitizer doses; the molecular and pharmacological reasons for the differences between 2 and 3 in vivo remain to be elucidated.In summary, our results provide a simple (classical) yet efficient approach to nonplanar perhalogenated phthalocyanines, of which [F 64 PcZn] is only the first representative. Other metals and R F groups will yield compounds with a diversity of size, shape, and depth of fluorinated cavities around a reactive metal center. Their thermal, photochemical, and chemical stability, coupled with their potential synthetic versatility and favorable solubility, suggest that this class of molecules might be effective for photophysical, chemical, and perhaps, medical uses. Applications requiring stability under harsh conditions and/or aggressive reagents, or solubility in nonconventional solvents might be considered. Experimental Section2: A mixture of zinc acetate (0.123 g, 0.668 mmol) and 1, (1.337 g, 2.67 mmol) was heated under Ar at 180 8C for 60 min. Chromatography on silica gel using 20 ± 30 % acetone/hexanes, followed by diffusion of hexanes into an acetone solution gave crystalline 2 in 21 % yield; m.p. > 300 8C; FAB MS [m/z] 2064.84 [M ]. Elemental analysis: calcd (%) for 13 C NMR (100.613 mHz, [D 6 ]acetone): d 154.6, 152.0, 130.9, 121.5, 117.5, 95.2. UV/Vis [nm] (log e), acetone, 322 (4.38), 396 (4.56), 620 (4.42), 686 (5.24).Biological tests: Suspensions of 2 or 3 in 10 % CRM (CRM cremofor) were administered intravenously. The tumors were illuminated with 650 ± 700 nm light (1 kW Xenon lamp, LL650 and LS700 filters) at fluence rates of 200 mW cm À2 , 400 J cm À2 per tumor. Absence of a palpable tumor three weeks post irradiation was considered regression.

show abstract

Reaktion von Acetyl‐Übergangsmetallkomplexen mit Phosphor‐Yliden – ein weiteres Beispiel zur Halogenid/Metallat‐Analogie

Cited by 21 publications

References 55 publications

Synthesis of acylphosphine complexes by controllable migration of acyl groups from molybdenum to phosphido ligands †

Synthesis of acylphosphine complexes by controllable migration of acyl groups from molybdenum to phosphido ligands †

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Synthesis and Structure of a Biconcave Cobalt Perfluorophthalocyanine and Its Catalysis of Novel Oxidative Carbon-Phosphorus Bonds Formation by Using Air

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