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[Cr(pincer2-)]2 as an electron shuttle for reductively promoted hydrazine disproportionation.
Dalton Trans 2019; 48(31):11642-11646DT

Abstract

We describe here delivery of hydrazine to a reducing, low oxidation state chromium bound to a proton responsive ligand which has already been deprotonated. Reaction of PhHNNH2 at a 4 : 1 mole ratio with the bis-(pyrazolate)pyridyl pincer ligated reducing agent [CrIIL]2 gives prompt conversion to [CrL2(PhNH2)2(μ-PhHNN)], with release of NH3 and C6H6, a new disproportionation of the hydrazine, with trapping of PhHNN as its dianion, bridging the two chromium centers. The redox balance of the reaction is discussed, and participation by Brønsted basic sites on the bis-(pyrazolate)pyridyl pincer ligand L2- is suggested, but no hydrazine protons remain on the pincer in the product.

Authors+Show Affiliations

Department of Chemistry, Indiana University, Bloomington, IN, USA. Caulton@indiana.edu.Department of Chemistry, Indiana University, Bloomington, IN, USA. Caulton@indiana.edu.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31310268

Citation

Labrum, Nicholas S., and Kenneth G. Caulton. "[Cr(pincer2-)]2 as an Electron Shuttle for Reductively Promoted Hydrazine Disproportionation." Dalton Transactions (Cambridge, England : 2003), vol. 48, no. 31, 2019, pp. 11642-11646.
Labrum NS, Caulton KG. [Cr(pincer2-)]2 as an electron shuttle for reductively promoted hydrazine disproportionation. Dalton Trans. 2019;48(31):11642-11646.
Labrum, N. S., & Caulton, K. G. (2019). [Cr(pincer2-)]2 as an electron shuttle for reductively promoted hydrazine disproportionation. Dalton Transactions (Cambridge, England : 2003), 48(31), pp. 11642-11646. doi:10.1039/c9dt02300c.
Labrum NS, Caulton KG. [Cr(pincer2-)]2 as an Electron Shuttle for Reductively Promoted Hydrazine Disproportionation. Dalton Trans. 2019 Aug 21;48(31):11642-11646. PubMed PMID: 31310268.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - [Cr(pincer2-)]2 as an electron shuttle for reductively promoted hydrazine disproportionation. AU - Labrum,Nicholas S, AU - Caulton,Kenneth G, Y1 - 2019/07/16/ PY - 2019/7/17/pubmed PY - 2019/7/17/medline PY - 2019/7/17/entrez SP - 11642 EP - 11646 JF - Dalton transactions (Cambridge, England : 2003) JO - Dalton Trans VL - 48 IS - 31 N2 - We describe here delivery of hydrazine to a reducing, low oxidation state chromium bound to a proton responsive ligand which has already been deprotonated. Reaction of PhHNNH2 at a 4 : 1 mole ratio with the bis-(pyrazolate)pyridyl pincer ligated reducing agent [CrIIL]2 gives prompt conversion to [CrL2(PhNH2)2(μ-PhHNN)], with release of NH3 and C6H6, a new disproportionation of the hydrazine, with trapping of PhHNN as its dianion, bridging the two chromium centers. The redox balance of the reaction is discussed, and participation by Brønsted basic sites on the bis-(pyrazolate)pyridyl pincer ligand L2- is suggested, but no hydrazine protons remain on the pincer in the product. SN - 1477-9234 UR - https://www.unboundmedicine.com/medline/citation/31310268/[Cr(pincer2-)]2_as_an_electron_shuttle_for_reductively_promoted_hydrazine_disproportionation L2 - https://doi.org/10.1039/c9dt02300c DB - PRIME DP - Unbound Medicine ER -