Chemistry of 0,+ (HL = 8-hydroxyquinoline): Synthesis, Structure, Metal Redox Behaviour and Isomer Selectivity

DOI: 10.1039/DT9950001417

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1417 - 1422 (1995)

Update date:2022-08-04

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Authors:

Menon, Mahua

Pramanik, Amitava

Bag, Nilkamal

Chakravorty, Animesh

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Article abstract of DOI:10.1039/DT9950001417

The reaction of with 8-hydroxyquinoline (HL) has afforded in two isomeric forms, one red and one yellow-green, the RuN2O2P2 co-ordination sphere being cis,trans,cis and trans,trans,trans respectively.Chemical or electrochemical oxidation of either isomer affords exclusively red-brown trans,trans,trans-(1+) isolated as the PF6(1-) salt.The latter complex is one-electron paramagnetic (low-spin t₂⁵) and in frozen glass (77 K) displays a rhombic EPR spectrum.Reduction of trans,trans,trans-PF6 by chemical or electrochemical means yields only trans,trans,trans-.X-Ray crystallography has been performed on cis,trans,cis- and trans,trans,trans-PF6*CH2Cl2.The Ru-O and Ru-N bond lengths decrease upon metal oxidation but the Ru-P bond length increases by ca. 0.15 Angrstroem (strong 4d?-3d? Ru(II)-P back-bonding).The reduction potential (Ru(III)-Ru(II)) order E_1/2(cis,trans,cis) > E_1/2(trans,trans,trans) corresponds to superior back-bonding in the cis- as compared to the trans-Ru(PPh3)2 motif.The stability of the observed geometry-valence combinations has been rationalised in terms of back-bonding, phosphine crowding and phenolato oxygen repulsion.

Full text of DOI:10.1039/DT9950001417

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