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$Research paper thumbnail of Palladium complexes bearing κ²-\u3ci\u3eN\u3c/i\u3e,\u3ci\u3eN\u3c/i\u3e and κ³-\u3ci\u3eN\u3c/i\u3e,\u3ci\u3eN\u3c/i\u3e,\u3ci\u3eO\u3c/i\u3e pendant amine bis(phenolate) ligands$

The synthesis and characterization of ten new palladium(II) amine bis(phenolate) complexes is rep... more The synthesis and characterization of ten new palladium(II) amine bis(phenolate) complexes is reported. Solution and single-crystal X-ray diffraction studies reveal the presence of both κ2-N,N and κ3-N,N,O binding modes in these square planar complexes. For complexes with sterically less demanding phenolate donors, addition of external acidic or basic reagents allows for the selective masking of a coordination site at Pd. Complexes bearing bulky cumyl substituents on phenolate donors exhibited unusual 1H NMR spectroscopic features that are consistent with an anagostic interaction with the palladium center. Computational analysis at the ωB97X-D/LAN2LDZ level of theory supported the assertion that such an anagostic interaction may play a role in stabilizing κ2 complexes bearing a cumyl-substituted amine bis(phenolate) ligand. X-ray crystallographic data for H21a-PdCl2, H22a-PdCl2, H1b-PdCl, H2b-PdCl, H1d-PdCl, and H1e-PdCl are reported

Chemical Science

Hanging on by a thread. Formally zerovalent copper complexes with an Al(iii) or Ga(iii) support w... more Hanging on by a thread. Formally zerovalent copper complexes with an Al(iii) or Ga(iii) support were investigated. The combined experimental and theoretical data corroborate the presence of an odd-electron σ-bond between Cu and the Group 13 center.

An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Angewandte Chemie International Edition, 2021

Pincer-type nickel-aluminum complexes were synthesized using two equivalents of the phosphinoamid... more Pincer-type nickel-aluminum complexes were synthesized using two equivalents of the phosphinoamide, [PhNCH2PiPr2]-. The Ni(0)-Al(III) complexes, {(MesPAlP)Ni}2(μ-N2) and {(MesPAlP)Ni}2(μ-COD), where MesPAlP is (Mes)Al(NPhCH2PiPr2)2, were structurally characterized. The (PAlP)Ni system exhibited cooperative bond cleavage mediated by the two-site Ni-Al unit, including oxidative addition of aryl halides, H2 activation, and ortho-directed C-H bond activation of pyridine N-oxide. One intriguing reaction is the reversible intramolecular transfer of the mesityl ring from the Al to the Ni site, which is evocative of the transmetalation step during cross-coupling catalysis. The aryl-transfer product,(THF)Al(NPhCH2PiPr2)2Ni(Mes), is the first example of a first-row transition metal aluminyl pincer complex. The addition of a judicious donor enables the Al metalloligand to convert reversibly between the alane and aluminyl forms via aryl group transfer to and from Ni, respectively. Theoretical calculations support a zwitterionic Niδ--Alδ+ electronic structure in the nickel-aluminyl complex.

ACS Catalysis, 2020

The Co(−I) dihydrogen complexes, [(η2-H2)CoML]−, where ML is the group 13 metalloligand, N(o-(NCH... more The Co(−I) dihydrogen complexes, [(η2-H2)CoML]−, where ML is the group 13 metalloligand, N(o-(NCH2PiPr2)C6H4)3M, and M is Al, Ga, or In, were previously reported ( J. Am. Chem. Soc. 2017, 139, 6570...

Macromolecules, 2020

The solid state and fluxional behaviors in solution of complexes L2AlOBn and L7AlOBn (Bn = benzyl... more The solid state and fluxional behaviors in solution of complexes L2AlOBn and L7AlOBn (Bn = benzyl) supported by an analog of salen incorporating indolide arms connected via their 2- and 7-positions...

ACS Catalysis, 2019

Simple Ti imido halide complexes such as [Br 2 Ti(N t Bu)py 2 ] 2 are competent catalysts for the... more Simple Ti imido halide complexes such as [Br 2 Ti(N t Bu)py 2 ] 2 are competent catalysts for the synthesis of unsymmetrical carbodiimides via Ti-catalyzed nitrene transfer from diazenes or azides to isocyanides. Both alkyl and aryl isocyanides are compatible with the reaction conditions, although product inhibition with sterically unencumbered substrates sometimes limits the yield when diazenes are employed as the oxidant. The reaction mechanism has been investigated both experimentally and computationally, wherein a key feature is that the product release is triggered by electron transfer from an η 2-carbodiimide to a Ti-bound azobenzene. This ligand-to-ligand redox buffering obviates the need for high-energy formally Ti II intermediates and provides further evidence that substrate and product "redox noninnocence" can promote unusual Ti redox catalytic transformations.

Inorganica Chimica Acta, 2019

J. Mater. Chem. A, 2017

The development of base-stable cationic groups for anion exchange membranes is important for appl... more The development of base-stable cationic groups for anion exchange membranes is important for application in alkaline fuel cells.