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2-Mercapto-1-t-butylimidazolyl as a Bridging Ligand: Synthesis and Structural Characterization of Nickel and Palladium Paddlewheel Complexes.

ABSTRACT: Nickel and palladium paddlewheel complexes that feature 2-mercapto-1-t-butylimidazolyl (mim(Bu(t) )) bridging ligands, namely Ni(2)[mim (Bu(t) )](4) and Pd(2)[mim (Bu(t) )](4), have been synthesized and structurally characterized by X-ray diffraction. Since the mim (Bu(t) ) ligand bridges in an asymmetric manner via a sulfur and nitrogen donor, paddlewheel compounds of the type M(2)[mim (Bu(t) )](4) may exist as isomers that are distinguished by the relative orientations of the ligands. In this regard, the (4,0)-Ni(2)[mim (Bu(t) )](4) and trans-(2,2)-Ni(2)[mim (Bu(t) )](4) isomers have been isolated for the nickel system, while the (4,0)-Pd(2)[mim (Bu(t) )](4) and (3,1)-Pd(2)[mim (Bu(t) )](4) isomers have been isolated for the palladium system.

SUBMITTER: Pang K

PROVIDER: S-EPMC2777662 | biostudies-literature | 2009 Sep

REPOSITORIES: biostudies-literature

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2-Mercapto-1-t-butylimidazolyl as a Bridging Ligand: Synthesis and Structural Characterization of Nickel and Palladium Paddlewheel Complexes.

Pang Keliang K Figueroa Joshua S JS Tonks Ian A IA Sattler Wesley W Parkin Gerard G

Inorganica chimica acta 20090901 12

Nickel and palladium paddlewheel complexes that feature 2-mercapto-1-t-butylimidazolyl (mim(Bu(t) )) bridging ligands, namely Ni(2)[mim (Bu(t) )](4) and Pd(2)[mim (Bu(t) )](4), have been synthesized and structurally characterized by X-ray diffraction. Since the mim (Bu(t) ) ligand bridges in an asymmetric manner via a sulfur and nitrogen donor, paddlewheel compounds of the type M(2)[mim (Bu(t) )](4) may exist as isomers that are distinguished by the relative orientations of the ligands. In this ...[more]

PMID: 20161357

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Project description:Metalation of the deprotonated dipyrrin (AdFL)Li with NiCl2(py)2 afforded the divalent Ni product (AdFL)NiCl(py)2 (1) (AdFL: 1,9-di(1-adamantyl)-5-perfluorophenyldipyrrin; py: pyridine). To generate a reactive synthon on which to explore oxidative group transfer, we used potassium graphite to reduce 1, affording the monovalent Ni synthon (AdFL)Ni(py) (2) and concomitant production of a stoichiometric equivalent of KCl and pyridine. Slow addition of mesityl- or 1-adamantylazide in benzene to 2 afforded the oxidized Ni complexes (AdFL)Ni(NMes) (3) and (AdFL)Ni(NAd) (4), respectively. Both 3 and 4 were characterized by multinuclear NMR, EPR, magnetometry, single-crystal X-ray crystallography, theoretical calculations, and X-ray absorption spectroscopies to provide a detailed electronic structure picture of the nitrenoid adducts. X-ray absorption near edge spectroscopy (XANES) on the Ni reveals higher energy Ni 1s → 3d transitions (3: 8333.2 eV; 4: 8333.4 eV) than NiI or unambiguous NiII analogues. N K-edge X-ray absorption spectroscopy performed on 3 and 4 reveals a common low-energy absorption present only for 3 and 4 (395.4 eV) that was assigned via TDDFT as an N 1s promotion into a predominantly N-localized, singly occupied orbital, akin to metal-supported iminyl complexes reported for iron. On the continuum of imido (i.e., NR2-) to iminyl (i.e., 2NR-) formulations, the complexes are best described as NiII-bound iminyl species given the N K-edge and TDDFT results. Given the open-shell configuration (S = 1/2) of the iminyl adducts, we then examined their propensity to undergo nitrenoid-group transfer to organic substrates. The adamantyl complex 4 readily consumes 1,4-cyclohexadiene (CHD) via H-atom abstraction to afford the amide (AdFL)Ni(NHAd) (5), whereas no reaction was observed upon treatment of the mesityl variant 3 with excess amount of CHD over 3 hours. Toluene can be functionalized by 4 at room temperature, exclusively affording the N-1-adamantyl-benzylidene (6). Slow addition of the organoazide substrate (4-azidobutyl)benzene (7) with 2 exclusively forms 4-phenylbutanenitrile (8) as opposed to an intramolecular cyclized pyrrolidine, resulting from facile β-H elimination outcompeting H-atom abstraction from the benzylic position, followed by rapid H2-elimination from the intermediate Ni hydride ketimide intermediate.

Dataset Information

2-Mercapto-1-t-butylimidazolyl as a Bridging Ligand: Synthesis and Structural Characterization of Nickel and Palladium Paddlewheel Complexes.

Publications

2-Mercapto-1-t-butylimidazolyl as a Bridging Ligand: Synthesis and Structural Characterization of Nickel and Palladium Paddlewheel Complexes.

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