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Geometrical Isomer Preference of RuII and RuIII: Chemistry and Structure of a RuS4P2 Family. Crystal Structure of

DOI: 10.1039/DT9900003823

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 3823 - 3828 (1990)

Update date:2022-09-26

Topics: Steric Effects   Coordination Environment  

Authors:

Pramanik, AmitavaPramanik, Amitava

Bag, NilkamalBag, Nilkamal

Lahiri, Goutam KumarLahiri, Goutam Kumar

Chakravorty, AnimeshChakravorty, Animesh

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Article abstract of DOI:10.1039/DT9900003823

The syntheses of mixed thioxanthate (trithiocarbonate)-phosphine complexes of types cis- (1) and trans-PF6 (2+) are reported (R=Et, Pri, or PhCH2).These along with trans- (2) and cis-+ (1+) constitute an electrochemically observable redox isomerisation cycle.The formal potentials of the couples (1+)-(1) and (2+)-(2) are ca. 0.65 and ca. 0.33 V respectively vs. saturated calomel electrode (s.c.e.).The isomerisation steps are (1+) --> (2+) (fast) and (2) --> (1) (k ca. 7.0*10-2 s-1).The X-ray stucture of complex (1; R=PhCH2) has been determined: space group C2/c, a=18.676(7), b=10.511(2), c=24.432(8) Angstroem, and Z=4.The superior stability of the cis configuration of RuII for complexes (1) arises from the strong back-bonding (cis > trans) within the Ru(PPh3)2 fragment.For RuIII, in which back-bonding is unimportant, the stable geometry is trans owing to favourable steric disposition of the PPh3 molecules.The frozen glass e.s.r. spectra of complexes (2+) have a sizable axial distortion (Δ ca. 8500 cm-1) with a relatively small rhombic component (V ca. 2200 cm-1).One of the two predicted transitions (ν1 ca. 7500 and ν2 ca. 9900 cm-1) within the t2g shell is observable (ν1 ca. 6500 cm-1) in the near-i.r. region.

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Product name:cis-bis(ethyl-trithiocarbamato-S,S')bis(triphenylphosphine)ruthenium(II)

Cas No:132140-63-7

132140-63-7

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