Anion/Naphthalenediimide Interactions in a Pd(II)-Based Tetrameric Metallocycle
A tetrameric metallocycle [Pd(dppp)(DPNDI)]4·8TfO consisting of four dppp-capped Pd(II) corners (dppp = 1,3-bis(diphenylphosphonium)propane) and four linear π-acidic N,N′-di(4-pyridyl)-1,4,5,8-naphthalene diimine (DPNDI) ligands has been synthesized, and its single-crystal structure has been...
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| Published in: | Crystal growth & design Vol. 19; no. 11; pp. 6017 - 6022 |
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| Main Authors: | , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
American Chemical Society
06-11-2019
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| Online Access: | Get full text |
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| Summary: | A tetrameric metallocycle [Pd(dppp)(DPNDI)]4·8TfO consisting of four dppp-capped Pd(II) corners (dppp = 1,3-bis(diphenylphosphonium)propane) and four linear π-acidic N,N′-di(4-pyridyl)-1,4,5,8-naphthalene diimine (DPNDI) ligands has been synthesized, and its single-crystal structure has been elucidated for the first time. The crystal structure of the metallocycle revealed anion−π, lone-pair−π, and CH···anion interactions between electron-deficient DPNDI ligands and TfO– counterions and provided valuable insights into its anion recognition and metathesis capabilities. The 1H, 19F, and 31P NMR studies demonstrated that in noncoordinating solvents, such as nitromethane and dichloromethane, the [Pd(dppp)(DPNDI)]4 8+ metallocycle underwent anion exchange in a single-crystal to single-crystal fashion without any structural changes. However, the metallocycle experienced slow dissociation in a polar solvent DMSO, which could be reversed easily by thermal treatment. |
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| ISSN: | 1528-7483 1528-7505 |
| DOI: | 10.1021/acs.cgd.9b00874 |