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Synthesis, characterization and redox properties of mixed phosphine nitroruthenium(II) complexes. Crystal structure of trans-[Ru(NO2)(terpy)-(PMe3)(PPh3)][ClO 4]·H2O

DOI: 10.1039/DT9960001463

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1463 - 1470 (1996)

Update date:2022-08-04

Topics:

Authors:

Szczepura, Lisa F.Szczepura, Lisa F.

Kubow, Stephen A.Kubow, Stephen A.

Leising, Randolph A.Leising, Randolph A.

Perez, Willie J.Perez, Willie J.

Huynh, My Hang VoHuynh, My Hang Vo

Lake, Charles H.Lake, Charles H.

Churchill, David G.Churchill, David G.

Churchill, Melvyn R.Churchill, Melvyn R.

Takeuchi, Kenneth J.Takeuchi, Kenneth J.

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Article abstract of DOI:10.1039/DT9960001463

The mixed phosphine complexes trans-[Ru(NO2)(terpy)(PMe3)(PR3)][ClO 4] (terpy = 2,2′:6′,2″-terpyridine; R = Et, Pr, Bz or Ph) were synthesized in high yields by a stepwise addition of each phosphine. These syntheses demonstrate the utility of ruthenium(II) in the preparation of mixed phosphine complexes. The stereochemistry of trans-[Ru(NO2)(terpy)(PMe3)(PPh3)][ClO 4]·H2O was confirmed by a single-crystal X-ray diffraction study. This species crystallizes in the monoclinic space group P21/c with a = 11.0199(15), b = 18.3888(28), c = 19.3089(25) A, β = 112.845(9)° and Z = 4. The two phosphine ligands are mutually trans, with P-Ru-P 177.5(1)°. The relative redox stabilities of the mixed phosphine complexes and a related series of trans-[Ru(NO2)(terpy)(PR3)2][ClO4] (R = Et, Pr, Bz or Ph) complexes were evaluated using cyclic voltammetric peak current ratios (ipc/ipa) for the ruthenium(III)-ruthenium(II) couples. The rate constants for nitroruthenium(III) decomposition were calculated from the ipc/ipa data and the contributions of electronic (E) and steric (S) factors to its rate of decomposition were determined using the relationship ln k - aE + bS + c. The average ratio of steric to electronic ligand effects on In k is approximately 30:70.

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Product name:RuCl(P(CH3)3)(P(CH2C6H5)3)(C15H11N3)(1+)*ClO4(1-) = [RuCl(P(CH3)3)(P(CH2C6H5)3)(C15H11N3)]ClO4

Cas No:176731-15-0

176731-15-0

R&D Labs maybe for 176731-15-0

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