Sterically variable dizinc complexes bearing bis(iminopyridyl)phenolate ligands: synthesis, structures and reactivity studies

Champouret, Yohan; Nodes, William J.; Scrimshire, Jason A.; Singh, Kuldip; Solan, Gregory A.; Young, Isla

doi:10.1039/b709385c

Cited by 8 publications

(1 citation statement)

References 58 publications

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“…In addition, these synthetic dizinc complexes have allowed new catalytic processes to be developed that are beyond the scope of natural enzymes. These processes include Mannich-type reactions, Aldol reactions, Friedel−Crafts alkylations, alkynylation reactions, as well as polymerization catalysis …”

Section: Introductionmentioning

confidence: 99%

Dinuclear Zinc Complexes Using Pentadentate Phenolate Ligands

2008

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The synthesis and characterization of 15 dinuclear zinc complexes are reported, including the X-ray crystal structures of 5 complexes. The ligand motif utilizing p-cresol as a bridging unit between the two zinc centers and a set of three related ligands has been synthesized; 2,6-bis(R)-p-cresol (where R is CH(2)NMe(CH(2))(2)NMe(2) = L(1), CH=N(CH(2))(2)NMe(2) = L(2), and CH(2)NH(CH(2))(2)NMe(2) = L(3)). Dizinc trihalide complexes [L(n)Zn(2)(mu-X)X(2)] (where X = Cl, Br, I) have been prepared. The trihalide complexes were treated with potassium ethoxide, resulting in quantitative substitution of the bridging halide group to give [L(n)Zn(2)(mu-OEt)X(2)]. The dizinc ethoxide complexes were tested in situ as initiators for lactide ring opening polymerization. Dizinc triacetate complexes have also been synthesized [L(n)Zn(2)(OAc)(3)], as well as cationic diacetate species containing two bridging acetate groups, [L(n)Zn(2)(mu-OAc)(2)][BPh(4)]. Structural differences between complexes of the three ligands are discussed.

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Section: Introductionmentioning

confidence: 99%

Dinuclear Zinc Complexes Using Pentadentate Phenolate Ligands

2008

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Iron(III) and Zinc(II) Calixarene Complexes: Synthesis, Structural Studies, and Use as Procatalysts for ε‐Caprolactone Polymerization

Arbaoui

Redshaw

Elsegood

et al. 2010

Chemistry An Asian Journal

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Treatment of the heterobimetallic iron(II) alkoxides [(THF)MFe(OtBu)(3)](2) with p-tert-butylcalix[4]areneH(4) (L(1)H(4)) affords the oxo-bridged diiron(III) complexes {Fe[M(NCMe)(x)](2)L(1)}(2)(mu-O), M = Na, x = 2 1 x 8(CH(3)CN), M = K, x = 3 2 x 3.5(CH(3)CN); similar use of p-tert-butylcalix[6]areneH(6) (L(2)H(6)) afforded [{Fe(2)(mu-O)Na(2)(OH(2))(NCMe)(2)L(2)}(2)][{Fe(2)(mu-O)Na(OH(2))(NCMe)(6)L(2)}(2)](2-)[Na(NCMe)(5)](2)(2+) 3 x 9.46(CH(3)CN) and [{Fe(2)(mu-O)L(2)(K(NCMe)(2))(2)}(2)] 4 x 10.8(MeCN), respectively. In the case of 4, a minor product {(L(2)(2)Fe(8)O(8))[K(NCMe)(1.5)K(H(2)O)(NCMe)(2.5)](2)} 5 x 6(CH(3)CN), which is comprised of chains of (L(2)(2)Fe(8)O(8)) clusters bridged by K/MeCN fragments, is also isolated. Use of p-tert-butylcalix[8]areneH(8) (L(3)H(8)) and two equivalents of [(THF)KFe(OtBu)(3)](2) affords [(K(2)(mu-NCCH(3))(4)(mu-OH(2)))(2)(Fe(2)(mu-O)L(3)H(2))(2)(CH(3)CN)(2)] 6 x 9(CH(3)CN). In the case of p-tert-butyltetrahomodioxacalix[6]areneH(6) (L(4)H(6)), reaction with [(THF)MFe(OtBu)(3)](2) (two equivalents) leads to isolation of the pseudoisomorphic complexes [M(2)(CH(3)CN)(4)L(4)Fe(2)(mu-O)] x 4 CH(3)CN M = Na 7 x 4(CH(3)CN), M = K 8 x 2(CH(3)CN); similar use of p-tert-butylhexahomotrioxacalix[3]areneH(3) (L(5)H(3)) led to [Na(2)Fe(2)(mu-OH)(2)(L(5))(2)(CH(3)CN)(4)] 9 x 2(CH(2)Cl(2)). The complex [L(4)(ZnEt)(4)Zn(2)(CH(3)CN)(4)(mu-OEt)(2)], 10 x 2(CH(3)CN), isolated from the reaction of L(4)H(6) and ZnEt(2) is also reported. Complexes 1-10 are structurally characterized (partially in the case of 4) and screened (not 5) as catalysts for the ring opening polymerization of epsilon-caprolactone.

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Phenol Based‐Ligands with Two Adjacent N,N′,O‐Binding Pockets

Wilting

Kügler

Siewert

2015

Zeitschrift anorg allge chemie

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The synthesis of three new ligands and their coordination behavior towards zinc ions with strongly coordinating anions and cobalt ions with weakly coordinating anions are reported. The ligands have two adjacent imidazolyl‐pyridinyl and pyrazolyl‐pyridinyl binding pockets, respectively, which are linked by a phenol unit. We also investigated the dynamic behavior of the ligand having the imidazolyl‐pyridiyl sidearm in solution. The reaction of the ligands and ZnCl2 yielded complexes of the type [LZn2Cl3]. When we used CoII salts with weakly coordinating anions, complexes of the general formula [L2Co2]2+ were formed.

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Sterically variable dizinc complexes bearing bis(iminopyridyl)phenolate ligands: synthesis, structures and reactivity studies

Cited by 8 publications

References 58 publications

Dinuclear Zinc Complexes Using Pentadentate Phenolate Ligands

Dinuclear Zinc Complexes Using Pentadentate Phenolate Ligands

Iron(III) and Zinc(II) Calixarene Complexes: Synthesis, Structural Studies, and Use as Procatalysts for ε‐Caprolactone Polymerization

Phenol Based‐Ligands with Two Adjacent N,N′,O‐Binding Pockets

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