New Alkyl−Cobalt(III) Complexes with Tridentate Amino−Oxime Ligands: Synthesis, Structure, and Reactivity

Dreos, Renata; Felluga, Alessandro; Nardin, Giorgio; Randaccio, Lucio; Siega, Patrizia; Tauzher, G.

doi:10.1002/1099-0682(20011)2001:1<267::aid-ejic267>3.0.co;2-z

Cited by 16 publications

(17 citation statements)

References 36 publications

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“…205 Studies on bis(imino) pyridine-ligated cobalt ethylene polymerisation catalysts have strongly indicated that the activated species is not the anticipated cobalt() alkyl cation. 206 Tridentate amino-oxime ligands have been used to support new Co() alkyl derivatives such as 41; 207 Electroluminescent organometallic Ir complexes containing fluorinated and cyclometalated aryl-pyridine and related ligands are being developed as processable, tuneable, highly efficient electroluminescent materials. 210 A series of trans-Rh(allenylidene) 2 complexes 43 show an unprecedented type of migratory insertion reaction where the unsaturated C 3 unit migrates into the Rh-O and Rh-C bonds of cis ligands.…”

Section: Cobalt Rhodium and Iridiummentioning

confidence: 99%

20 Organometallic chemistry of monometallic species

Arnold

2002

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Section: Cobalt Rhodium and Iridiummentioning

confidence: 99%

20 Organometallic chemistry of monometallic species

Arnold

2002

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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“…have been extensively studied [38][39][40][41][42][43]. Binuclear complexes of 4-(2-amino-4-methylphenolisonitrosoacetyl)biphenyl were synthesized and characterized [42].…”

Section: Introductionmentioning

confidence: 99%

Syntheses, structures and catalase-like activities of mono-, tri- and pentanuclear Cu(II), Cu(II)-Co(II) complexes with cyanide and ONO tridentate oxime ligand

Karipçin

Culu

Sharma³

et al. 2013

Main Group Chemistry

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A novel cyanide containing mononuclear copper(II) oxime complex K[CuL(CN)] (1) was synthesized as a starting material to make new polynuclear complexes. Trinuclear complexes K 2 [{CuL(NC)} 2 (ML)] (M = Co(II) (2), Cu(II) (3) and pentanuclear complexes K 2 [{CuL(NC)} 4 M] (M = Co(II) (4), Cu(II) ( 5)) of 4-(2-amino-4-methylphenolisonitrosoacetyl)biphenyl (H 2 L) have been synthesized and characterized by elemental analysis, molar conductance, FT-IR, magnetic data. The lowest energy model structures of the ligand and its mononuclear Cu(II) complex have been determined by MOPAC 2007 program using PM6 method. Catalytic activities of the complexes for the disproportionation of hydrogen peroxide were investigated in the presence of imidazole. The multinuclear Cu(II)-Co(II) complexes (2, 4) display efficiency in disproportion reactions of hydrogen peroxide producing water and dioxygen in catalase-like activity.

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“…A useful model, which may be applied to study the trans effect in alkylcobalamins is represented by complexes of the type [Co(LNHpy)(HLNHpy)R] + (R = Et, Me, CF 3 CH 2 and bridging-CH 2 , HLNHpy = 2-(2-pyridylethyl)amino-3butanone oxime and LNHpy − its conjugate base). 26 In these models the pyridyl trans to the alkyl group, is covalently linked to the equatorial system by an ethylenic chain. It was found that the second order rate constants for the substitution of pyridyl by cyanide (a reaction reminiscent of the replacement of benzimidazole in cobalamins) are 19.1, 0.25, 2.2 × 10 −2 and 1.7 × 10 −2 M −1 s −1 for R = Et, Me, CF 3 CH 2 and bridging-CH 2 , respectively.…”

Section: Introductionmentioning

confidence: 99%

Kinetic and mechanistic study on the reaction of alkylcobaloximes with azoles

et al. 2004

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The kinetics of axial water substitution by azoles (pyrazole and 1,2,4-triazole) in three different cobaloximes, viz.trans-[Co(Hdmg)(2)(R)H(2)O] where Hdmg = dimethylglyoximate, R = PhCH(2), Et and CF(3)CH(2), were studied as a function of azole concentration, temperature and pressure in aqueous solution. The second order rate constants for the substitution of water in trans-[Co(Hdmg)(2)(R)H(2)O] for R = Et at pH 6.0, 25 degrees C and I= 0.1 M (NaClO(4)), were found to be 1309 and 1200 M(-1) s(-1) for pyrazole (Pz) and 1,2,4-triazole (Tz), respectively, and those obtained for R = PhCH(2) were found to be 755 and 691 M(-1) s(-1), respectively. The second order rate constants in the case of R = CF(3)CH(2) were found to be 0.358 and 0.348 M(-1) s(-1) for Pz and Tz, respectively. The relative order of reactivity for the different alkyls being Et > PhCH(2) > CF(3)CH(2). The activation parameters (DeltaH([not equal]), DeltaS([not equal]) and DeltaV([not equal])) obtained for these reactions were found to be in the range of 65-87 kJ mol(-1), 24-47 J mol(-1) K(-1) and 2.5-7.7 cm(3) mol(-1), respectively. These data suggest that an I(d) substitution mechanism operates where the azoles participate in the transition state.

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New Alkyl−Cobalt(III) Complexes with Tridentate Amino−Oxime Ligands: Synthesis, Structure, and Reactivity

Cited by 16 publications

References 36 publications

20 Organometallic chemistry of monometallic species

20 Organometallic chemistry of monometallic species

Syntheses, structures and catalase-like activities of mono-, tri- and pentanuclear Cu(II), Cu(II)-Co(II) complexes with cyanide and ONO tridentate oxime ligand

Kinetic and mechanistic study on the reaction of alkylcobaloximes with azoles

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