Ligand Influence on Metal Aggregation: a Unique Bonding Mode for Pyridylpyrrolides

Andino, José G.; Flores, Jaime A.; Karty, Jonathan A.; Massa, Joseph; Park, Hyunsoo; Tsvetkov, Nikolay P.; Wolfe, Robert; Caulton, Kenneth G.

doi:10.1021/ic100878s

Cited by 18 publications

(38 citation statements)

References 13 publications

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“…We confirmed that we have synthesized the same HL 1 as obtained earlier, by identity of the NMR chemical shifts. We have also reported the crystal structure of HL 1 itself, showing this same, corrected connectivity (Scheme ).…”

Section: Methodsmentioning

confidence: 52%

Probing Redox Noninnocence of Copper and Zinc Bis‐pyridylpyrrolides

et al. 2018

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A series of complexes of divalent copper and zinc carrying two systematically substituted 2,2′‐pyridylpyrrolide ligands, designated Ln to indicate the number of pyrrole CF3 substituents (n = 0, 1, 2), have been studied for their geometric and electronic structures. These reveal the pyridylpyrrolide to be a highly anisotropic nitrogen donor ligand which distorts ML2 complexes away from both planar and tetrahedral structures. Characterization includes CV and mass spectrometry, which show access to cations beyond conventional maximum metal oxidation states. EPR studies at multiple microwave frequencies of the series Cu(Ln)2 gave insight into the substituent effect on frontier orbital composition of these complexes. While Cu(L2)2 exhibited EPR spectra that were roughly comparable to those for typical, tetragonally distorted CuII complexes with the SOMO having dx²–y² character, the other two complexes exhibited more unusual EPR spectra indicative of their distinct geometry, reminiscent of equatorially‐vacant trigonal bipyramidal hybridization and fully consistent with the X‐ray crystal structure determinations of all three Cu(Ln)2. DFT calculations map both geometric and delocalization changes upon redox change, and show the relevance of oxidation at the pyrrolide donors rather than at the metal.

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Section: Methodsmentioning

confidence: 52%

Probing Redox Noninnocence of Copper and Zinc Bis‐pyridylpyrrolides

et al. 2018

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“…Consequently, trans-2 was chemically reduced to [2] − by cobaltocene (E 1/2 = −1.33 V vs FcH/[FcH] + ) 50 giving the diamagnetic cobaltocenium cuprate [CoCp 2 ][2] (Scheme 1) which was characterized by NMR, IR, and UV−vis spectroscopy as well as by mass spectrometry and elemental analysis (Experimental Section and Supporting Information, Figures S7−S10). The related cuprate K[CuL 1 2 ] with pyridylpyrrolido ligands [L 1 ] − has been prepared from Cu 3 L 1 3 39 and potassium and characterized by NMR spectroscopy and mass spectrometry. 51 A less than four-coordinate structure has been suggested for K[CuL 1 2 ].…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Photochemistry and Redox Chemistry of an Unsymmetrical Bimetallic Copper(I) Complex

et al. 2016

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The bimetallic copper(I) complex CuL (cis-1) is formed with high diasteroselectivity from [Cu(NCCH)][BF] and HL (4-tert-butyl phenyl(pyrrolato-2-yl-methylene)amine) in a kinetically controlled reaction. cis-1 features a rather short Cu···Cu distance of 2.4756(6) Å and is weakly emissive at room temperature in solution. Oxidatively triggered disproportionation of cis-1 yields elemental copper and the mononuclear copper(II) complex CuL (trans-2). One-electron reduction of trans-2 gives cuprate [2] with a bent bis(pyrrolato) coordinated copper(I) entity. The imine donor atoms of [2] can insert an additional copper(I) ion giving exclusively the bimetallic complex cis-1 closing the oxidation-elimination-reduction-insertion cycle.

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“…This core structure is quite similar to those of Ag 3 N-heterocyclic carbene complexes, [Ag 3 (CH 3 im(CH 2 py)) 3 -(NCCH 3 ) 2 ] 3− , [Ag 3 (im(CH 2 py) 2 ) 3 ] 3− and [Ag 3 (im(CH 2 Mepy) 2 ) 3 ] 3− , 22,23 and Cu 3 monopyridylpyrrole complex. 24,25 Short Ag-Ag distances in 1 (Ag1-Ag2 2.9370(12) Å, Ag1-Ag3 2.8732(13) Å, Ag2-Ag3 2.8937(13) Å) due to the silver-silver interaction are slightly longer than av. 2.784 Å observed in Ag 3 N-heterocyclic carbene complexes.…”

Section: Description Of Structurementioning

confidence: 99%

Multi-nuclear silver(i) and copper(i) complexes: a novel bonding mode for bispyridylpyrrolides

Liang

et al. 2014

Dalton Trans.

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Reaction of deprotonated 2,5-bis(2'-pyridyl)pyrrole (HPDPH) with AgOTf (where OTf(-) = triflato) in THF readily yields a yellow triangular Ag3 complex [(PDPH)Ag]3 (1), of which the av. AgAg distance is 2.902 Å. A mixture of HPDPH and AgOTf reacts with PPh3 to afford a linear Ag3 complex [Ag{(PDPH)Ag(PPh3)}2](OTf) (2·OTf), whereas it reacts with diethyl phosphite in the presence of Li[N(SiMe3)2] to yield a di-nuclear complex Li2[(PDPH)Ag2{P(O)(OEt)2}2](OTf) (Li2·3·OTf). In 2, the terminal Ag atoms are three coordinate containing one phosphorous atom from PPh3 and two nitrogen atoms of the PDPH ligand. The center Ag atom is only two coordinate, binding to the residued pyridyl N atom of the PDPH ligand. In 3, two silver atoms are bridged by one PDPH ligand. Treatment of PDPH with CuCl in the presence of NaH afforded a heterobimetallic copper-sodium complex [Cu(PDPH)2Na(thf)2] (4). The PDPH ligand in 1-4 is nonplanar, with torsion angles between pyridine and pyrrole rings in the range of 15.8-38.3°. The argentophilic interactions, π∙∙∙π stacking, and weak interaction of Ag∙∙∙C(aromatic) are observed in these complexes. Interestingly, treatment of the analogous 2,5-bis(6'-bromo-2'-pyridyl)pyrrole (HPDPBr) with AgOTf affords a di-nuclear complex [(HPDPBr)Ag]2(OTf)2 (5·(OTf)2). Its HPDPBr ligands coordinate to Ag atoms in a head-to-head fashion, and two protonated pyrrole linkages reside in the anti-parallel direction and are non-coordinating. Short AgBr distances of 3.255-3.390 Å are observed.

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Ligand Influence on Metal Aggregation: a Unique Bonding Mode for Pyridylpyrrolides

Cited by 18 publications

References 13 publications

Probing Redox Noninnocence of Copper and Zinc Bis‐pyridylpyrrolides

Probing Redox Noninnocence of Copper and Zinc Bis‐pyridylpyrrolides

Photochemistry and Redox Chemistry of an Unsymmetrical Bimetallic Copper(I) Complex

Multi-nuclear silver(i) and copper(i) complexes: a novel bonding mode for bispyridylpyrrolides

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