Copper(II) Complexes of N‐Methylated Derivatives of ortho‐ and meta‐Xylyl‐Bridged Bis(1,4,7‐triazacyclononane) Ligands: Synthesis, X‐ray Structure and Reactivity as Artificial Nucleases

Belousoff, Matthew J.; Graham, Bimbil; Spiccia, Leone

doi:10.1002/ejic.200800533

Cited by 17 publications

(14 citation statements)

References 47 publications

(52 reference statements)

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“…The apical Cu–N bond lengths ([ 8 ], Cu–N12 2.102(2) Å; [ 9 ], Cu–N21 2.106(2) Å) are significantly longer than the Cu–N bond distances involving the basal nitrogen donors ([ 8 ], Cu–N3 1.967(2) Å and Cu–N21 1.976(2) Å; [ 9 ], Cu–N3 1.965(2) Å and Cu–N12 1.967(2) Å). These values fall within the range observed for related square-pyramidal copper(II) complexes featuring a CuN 3 OAc donor set with an identical arrangement of the donors . The coordination geometry of pentacoordinated metal centers such as the copper(II) ion in [ 8 ] and [ 9 ] can be described using the τ value .…”

Section: Results and Discussionmentioning

confidence: 62%

Synthesis of Heterobimetallic Complexes by Coordination of Rhodium(III) and Iridium(III) Poly-N,O-NHC Complexes to Silver(I), Copper(II), and Zinc(II)

et al. 2018

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The reaction of [RhCl 2 (Cp*)] 2 with 2-trimethylsiloxyphenyl isocyanide (1) led to the mononuclear diisocyanide complex [RhCl(Cp*)(1) 2 ]. Cleavage of the Si− O bonds of the coordinated isocyanide ligands with a catalytic amount of KF and H 2 O gave the neutral rhodium(III) complex [RhCl(Cp*)(NH,O-NHC)(N,O-NHC)] ([2]) bearing a C2metalated N,O-benzoxazolinato ligand and an NH,O-benzoxazolin-2-ylidene ligand. In the presence of AgBF 4 the same reaction sequence with [MCl 2 (Cp*)] 2 (M = Rh, Ir) and 1 led to the removal of all halogeno ligands and formation of the complexes [M(Cp*)(NH,O-NHC)(N,O-NHC) 2 ] (M = Rh, [3]; M = Ir, [4]) bearing one C-metalated NH,O-NHC benzoxazolin-2-ylidene and two C-metalated N,O-benzoxazolinato ligands. Deprotonation of the remaining N−H function in complexes [3] and [4] generated complexes with three amido donor functions which act as tripodal metalloligands for the coordination to additional transition metals such as Ag I , Cu II , and Zn II , thus allowing the preparation of the polynuclear heterobimetallic complexes [5]−[10] bearing C/N-metalated benzoxazolinato ligands.

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Section: Results and Discussionmentioning

confidence: 62%

Synthesis of Heterobimetallic Complexes by Coordination of Rhodium(III) and Iridium(III) Poly-N,O-NHC Complexes to Silver(I), Copper(II), and Zinc(II)

et al. 2018

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“…[31][32][33] Although ligands with 2, 3 or 4 tacn moieties linked by a phenyl group have been reported previously, in no case was a discrete trinuclear metal complex formed having a central phosphate bridge. [34][35][36][37][38][39][40] Reaction of L1 with CuCl 2 in the presence of HPO 4 2under ambient conditions gave a clear blue solution after filtration. Addition of NH 4 (PF 6 ) to this clear solution and subsequent evaporation in air afforded crystalline prisms of [(Cu II Cl) 3 -(HPO 4 )L1](PF 6 ) (1).…”

mentioning

confidence: 99%

“…We therefore placed three 1,4,7-triazacyclononane (tacn) ligand arms at the meta positions of the tribenzylamine platform, and this effort gave the novel tris-tacn tripodal cluster-forming ligand, N(CH 2 - m -C 6 H 4 -CH 2 tacn) 3 ( L1 ) (syntheses and details in the Supporting Information). The choice of tacn ligand arms was based on the well-known facial coordination and high binding affinity of this unit for most transition metals. − Although ligands with two, three, or four tacn moieties linked by a phenyl group have been reported previously, in no case was a discrete trinuclear metal complex formed having a central phosphate bridge. − …”

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confidence: 99%

Tripodal Tris-tacn and Tris-dpa Platforms for Assembling Phosphate-Templated Trimetallic Centers

2010

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Multidentate tripodal ligands, N(CH2-m-C6H4-CH2tacn)3 (L1) and N(CH2-o-C6H4-CH2N(CH2py)2)3 (L2), have been devised for assembling high-nuclearity metal clusters. By using the same tripodal platform with different ligand appendages, either triazacyclononanes or dipicolylamines, and functionalizing either the ortho or the meta positions on the tris(xylyl) linker arms, discrete trimetal phosphate units of relevance to phosphate-metabolizing trimetallic centers in biology were prepared. Four such compounds, [(Cu(II)Cl)3(HPO4)L1](PF6) (1), [(Cu(II)Cl)3(HAsO4)L1](PF6) (2), Na2[Mn(III)6Mn(II)2(H2O)2(HPO4)6(PO4)4(L1)2] (3), and [Co(II)3(H2PO4)Cl2(MeCN)L2](PF6)3 (4), all containing three metal centers bound to a central phosphate or arsenate unit bridging oxygen atoms, have been synthesized and structurally characterized. These results demonstrate the propensity of this novel tripodal ligand platform, in the presence of phosphate or arsenate, to assemble {M3(EO4)} units and thus structurally mimic trimetallic active sites of proteins involved in phosphate metabolism. Reactivity studies reveal that the tricopper complex 1 is more efficient than monocopper analogues in catalyzing the hydrolysis of 4-nitrophenyl phosphate.

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“…The current structures can be compared with those of metal complexes of the analogous m-xylene bridged bis(tacn) ligand 1,3-bis(1,4,7-triazacyclonon-1-ylmethylene)benzene (L mx ). [10,[22][23][24][25][26] In these m-xylenyl structures, the L mx ligand is able to bind to two disconnected metal centres or alternatively, encapsulate a M 2 (m-X) 2 moiety (Fig. 5a), similar to the L pyx ligand reported here.…”

Section: Resultsmentioning

confidence: 70%

Bi-Nuclear Metal Complexes of 2,6-Bis(1,4,7-triazacyclonon-1-yl-methylene)pyridine with Zinc(II), Copper(II), and Nickel(II)

et al. 2015

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The coordination chemistry of 2,6-bis(1,4,7-triazacyclonon-1-ylmethyl)pyridine (L pyx , 1) has been investigated and shown to yield bi-nuclear metal complexes in the presence of zinc(II), copper(II), or nickel(II) ions. . In all cases, the L pyx ligand binding is unsymmetrical between the two metal centres being tridentate to one and tetradentate to the other through an additional coordination of the pyridyl linker.

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Copper(II) Complexes of N‐Methylated Derivatives of ortho‐ and meta‐Xylyl‐Bridged Bis(1,4,7‐triazacyclononane) Ligands: Synthesis, X‐ray Structure and Reactivity as Artificial Nucleases

Cited by 17 publications

References 47 publications

Synthesis of Heterobimetallic Complexes by Coordination of Rhodium(III) and Iridium(III) Poly-N,O-NHC Complexes to Silver(I), Copper(II), and Zinc(II)

Synthesis of Heterobimetallic Complexes by Coordination of Rhodium(III) and Iridium(III) Poly-N,O-NHC Complexes to Silver(I), Copper(II), and Zinc(II)

Tripodal Tris-tacn and Tris-dpa Platforms for Assembling Phosphate-Templated Trimetallic Centers

Bi-Nuclear Metal Complexes of 2,6-Bis(1,4,7-triazacyclonon-1-yl-methylene)pyridine with Zinc(II), Copper(II), and Nickel(II)

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