Complexes bearing an enantiopure N,N,O scorpionate ligand derived from (−)-menthone

Peters, Liv; Burzlaff, Nicolai

doi:10.1016/j.poly.2003.11.038

Cited by 44 publications

(22 citation statements)

References 24 publications

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“…In contrast, related monoalkyl heteroscorpionate magnesium complexes [35] readily give the corresponding sandwich units. Burzlaff and Hegelmann also described the preparation of a series of ruthenium complexes by using the aforementioned enantiopure facially-binding tripod NNO-ligands bis(camphorpyrazol-1-yl)acetic acid (Hbpa 4cam ) and bis(menthylpyrazol-1-yl)acetic acid (Hbpz 4meth [9] These processes gave complexes in yields of around 70 %.…”

Section: 2(b) Complexes Of Late Transition Metals and Znmentioning

confidence: 99%

“…Inversion of the configuration at the tetrahedral bridging atom yields identical compounds. This methodology was used to obtain a series of enantiopure chiral C 2 -symmetric bis(pyrazol-1-yl)methane derivatives by the treatment of CH 2 Cl 2 with a pyrazole ring fused to camphor [8] or menthone [9] in a two-phase system (Scheme 5). In both cases, the three possible structural isomers were obtained but only one isomer (C or F) could exclusively be deprotonated at the methylene bridge with nBuLi.…”

Section: 1(b) Introduction Of Chirality By the Use Of Enantiopure mentioning

confidence: 99%

“…[10] After isolation the compounds were deprotonated with nBuLi and the subsequent treatment with carbon dioxide and acidic workup yielded tripodal and enantiopure bis(pyrazol-1-yl)acetic acid derivatives in a yield of about 60 % (Scheme 6). [8,9] An enantiopure NNO-scorpionate ligand was recently synthesized by Burzlaff et al [11] using the C 2 -symmetric 2,2Ј-carbonyl(camphorpyrazole) or 2,2Ј-sulfinylbis(camphorpyrazole) compounds. The reaction of camphorpyrazole with triphosgene under reflux in toluene or benzene gave only the C 2 -symmetrical compound in very high yield (Scheme 7).…”

Section: 1(b) Introduction Of Chirality By the Use Of Enantiopure mentioning

confidence: 99%

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Recent Advances in the Design and Coordination Chemistry of Heteroscorpionate Ligands Bearing Stereogenic Centres

et al. 2008

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Section: 2(b) Complexes Of Late Transition Metals and Znmentioning

confidence: 99%

Section: 1(b) Introduction Of Chirality By the Use Of Enantiopure mentioning

confidence: 99%

Section: 1(b) Introduction Of Chirality By the Use Of Enantiopure mentioning

confidence: 99%

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Recent Advances in the Design and Coordination Chemistry of Heteroscorpionate Ligands Bearing Stereogenic Centres

et al. 2008

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“…[5][6][7][8] Complexes of these versatile N,N,O donor ligands with various transition metal complexes reveal their potential in coordination chemistry as scorpionate ligands closely related to hydrotris(pyrazol-1-yl)borate (Tp). [5,6,9,10] The N,N,O binding motif is of particular interest not only as tripodal ligand in organometallic and coordination chemistry but as mimic of the active site of enzymes with a 2-His-1-carboxylate motif as well.…”

Section: Introductionmentioning

confidence: 99%

Novel N,N,O Scorpionate Ligands and Transition Metal Complexes Thereof Suitable for Polymerisation

et al. 2008

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Esterification of 2,2‐bis(3,5‐dimethylpyrazol‐1‐yl)‐3‐hydroxypropionic acid (2) with methacryloyl chloride led to the new κ3‐N,N,O ligand 2,2‐bis(3,5‐dimethylpyrazol‐1‐yl)‐3‐methacrylato‐propionic acid (Hbdmpzmp) (3). The κ3‐N,N,O coordination as known from bis(3,5‐dimethylpyrazol‐1‐yl)acetic acid (Hbdmpza, 1) was proven by syntheses of the complexes [Mn(bdmpzmp)(CO)3] (4) and [Re(bdmpzmp)(CO)3] (5) and the single‐crystal X‐ray structure of 4. The methacrylic ester functionality makes 3, 4 and 5 suitable for polymerisation. Thus, copolymerisation of 3 with methyl methacrylate (MMA), a combination of MMA and ethylene glycol dimethacrylate (EGDMA) or pure EGDMA led to various solid phases (P1a–P1c, P2, P3a, P3b) with incorporated ligand. Polymer‐bound manganese and rhenium tricarbonyl complexes could be obtained by copolymerisation of 4 and 5 with MMA as well as by a polymer analogous reaction of P1a with appropriate metal salts. In both cases, the facial tripodal binding behaviour was evidenced by IR spectra of the polymer supported transition metal complexes and the uptake of manganese was proven by AAS measurements. Reaction of the soluble deprotonated solid phase P1a with copper(II) chloride led to a deep‐blue solid phase (P‐Cu‐I). The UV/Vis absorption maximum at 715 nm indicates the copper centres to act as crosslinking agent by a similar binding behaviour as in [Cu(bdmpza)2]. In contrast, the heterogeneous reaction of P1b with copper(II) chloride formed a lime‐green solid phase (P‐Cu‐II). The bathochromic shift of the absorption maximum by 78 nm suggests one‐sided bound copper centres. EPR spectra do not show exchange narrowing between the copper centres indicating the metal centres to be far enough apart from each other to prevent magnetic interactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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“…Reaction of Na Our recent work focuses on derivatives of such N,N,O ligands, to broaden the field of available heteroscopionate ligands with various electronic and steric properties. So far examples of chiral bis(1H-pyrazol-1-yl)acetic acids, [10] 3,3-bis(imidazol-2-yl)propionic acids [11] or 2-[bis(1H-pyrazol-1-yl)methyl]phenolates [12] have been obtained. Moreover, tricarbonylrhenium complexes are of particular interest as model compounds for radiopharmaceutical applications.…”

Section: Introductionmentioning

confidence: 99%

N,N,O Ligands Based on Triazoles and Transition Metal Complexes Thereof

et al. 2010

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The reaction of 2H-benzotriazole (1) with dichloroacetic acid leads to the symmetric bis(2H-benzotriazol-2-yl)methane (2c) in 40 % yield. Deprotonation of 2c at the bridging methylene group and subsequent carboxylation with CO 2 yielded the new tripodal N,N,O ligand bis(2H-benzotriazol-2-yl)acetic acid Hbbta (3). The sterically less demanding sodium 3,3-bis(1H-1,2,4-triazol-1-yl)propionate Na[btp] (5) was obtained by saponification of methyl 3,3-bis(1H-1,2,4-triazol-1-yl)propionate (4). The heteroscorpionate ligand 3 was treated with [MnBr(CO) 5 ] and [RuCl 2 (PPh 3 ) 3 ] to form the manganese tricarbonyl complex [Mn(bbta)(CO) 3 ] (6) and the air stable ruthenium complex [Ru(bbta)Cl(PPh 3 ) 2 ] (7). DFT calculations and the IR spectra of the carbonyl complex 6 reveal ligand 3

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Complexes bearing an enantiopure N,N,O scorpionate ligand derived from (−)-menthone

Cited by 44 publications

References 24 publications

Recent Advances in the Design and Coordination Chemistry of Heteroscorpionate Ligands Bearing Stereogenic Centres

Recent Advances in the Design and Coordination Chemistry of Heteroscorpionate Ligands Bearing Stereogenic Centres

Novel N,N,O Scorpionate Ligands and Transition Metal Complexes Thereof Suitable for Polymerisation

N,N,O Ligands Based on Triazoles and Transition Metal Complexes Thereof

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