Very strong trans effect in ruthenacyclic carbamoyl complexes leads to ligand redistribution in phosphine derivatives

Barik, Chandan Kr; Ganguly, Rakesh; Li, Yongxin; Leong, Weng Kee

doi:10.1016/j.jorganchem.2019.02.022

Cited by 3 publications

(1 citation statement)

References 36 publications

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“…Recently, we have discovered that for some of these compounds, which were often obtained with the cycloruthenated 2-phenylpyridine (abbr. phpy ), acetonitrile and other ancillary ligands such as phenanthroline or polypyridines do display interesting properties as they isomerize under mild conditions in such a way that an acetonitrile moves from a position trans to N to a position trans to C of the cycloruthenated phpy unit . Recently, related strong trans effects were reported in ruthenacyclic carbamoyl complexes .…”

Section: Introductionmentioning

confidence: 99%

Follow-Up Study of Trans-C to Cis-C Thermally or Photochemically Induced Isomerization of Terpyridine Adducts of Cycloruthenated 2-Aryl-2′-pyridine Compounds

Ali,

Cornaton,

Djukic

et al. 2024

Inorg. Chem.

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The mechanism of isomerization of the known 2-phenyl,pyridine (phpy) derivatives [Ru(phpy-κC,N) (MeCN-trans-N)(terpy)]PF 6 , 2, to [Ru-(phpy-κC,N)(MeCN-trans-C)(terpy)]PF 6 (terpy = 2,2′;6′,2″-terpyridine), 3, at temperatures >50 °C has been investigated both by 1 H NMR spectroscopy and by DFT calculations. The photoisomerization of 2 to 3 by UV light occurred also quantitatively in MeCN after 20 h at room temperature. A similar behavior to that of 2 could be established for the related compound [Ru(3-acridine-2′-C 5 H 4 N-κC,N)(MeCN-trans-N)(2,2′;6′,2″-terpyridine)]PF 6 , 6 (acridine = dibenzo[b,e]pyridine or 2,3-benzoquinoline), that was obtained from the reaction between [Ru(3-acridine-2′-C 5 H 4 N-κC,N) (MeCN) 4 ]PF 6 , 4, and terpy in MeOH/MeCN at 60 °C for 24 h. Similar to 2, the isomerization of 6 to [Ru(3-acridine-2′-C 5 H 4 N-κC,N)(MeCN-trans-C) (terpy)]PF 6 , 7, could be induced thermally (48 h at 60 °C in pure MeOH) or photochemically under UV radiation in MeCN at room temperature. A compound closely related to 7 but in which MeCN was replaced by H 2 O was described earlier (Tanaka et al. Inorg. Chem. 2012, 51, 5386−539). The presence of water on this compound had a dramatic effect as far as the coordination of terpy was concerned as its isomerization to a compound related to 6 (in which H 2 O instead of MeCN is coordinated to Ru) occurred indeed photochemically via irradiation with visible light.

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Section: Introductionmentioning

confidence: 99%

Follow-Up Study of Trans-C to Cis-C Thermally or Photochemically Induced Isomerization of Terpyridine Adducts of Cycloruthenated 2-Aryl-2′-pyridine Compounds

Ali,

Cornaton,

Djukic

et al. 2024

Inorg. Chem.

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Ruthenium‐Based Structural Mimics of the Cofactor of [Fe]‐Hydrogenase: Replacement of the Acyl Moiety with an N‐Heterocyclic Carbene

et al. 2020

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A synthetic route is reported towards ruthenium‐based structural mimics of the [Fe]‐hydrogenase metal cofactor in which the acyl moiety is replaced by an N‐heterocyclic carbene. It is observed that the pyridyl‐NHC ligand has a rather different trans influence from that of a simple NHC in their ruthenium derivatives. The basis for this difference is explored crystallographically and computationally, and it accounts for their different behaviour towards thiolation.

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Ruthenacyclic carbamoyl mimics of the [Fe]-hydrogenase active site: Derivatisation at the 4-position of the pyridinyl ring

et al. 2021

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Very strong trans effect in ruthenacyclic carbamoyl complexes leads to ligand redistribution in phosphine derivatives

Cited by 3 publications

References 36 publications

Follow-Up Study of Trans-C to Cis-C Thermally or Photochemically Induced Isomerization of Terpyridine Adducts of Cycloruthenated 2-Aryl-2′-pyridine Compounds

Follow-Up Study of Trans-C to Cis-C Thermally or Photochemically Induced Isomerization of Terpyridine Adducts of Cycloruthenated 2-Aryl-2′-pyridine Compounds

Ruthenium‐Based Structural Mimics of the Cofactor of [Fe]‐Hydrogenase: Replacement of the Acyl Moiety with an N‐Heterocyclic Carbene

Ruthenacyclic carbamoyl mimics of the [Fe]-hydrogenase active site: Derivatisation at the 4-position of the pyridinyl ring

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