Reduction-oxidation properties of organo-transition metal complexes. Part 33. Ligand-vs. metal-based oxidation of cyano-bridged catecholatoruthenium–manganese carbonyl compounds: the X-ray crystal structure of cis-[(dppe)(Et3P)(OC)2Mn(µ-CN)Ru(CO)2(PPh3)(o-O2C6Cl4)]·CH2Cl2

Christofides, Aristides; Connelly, Neil G.; Lawson, Holly J.; Loyns, Andrew C.; Orpen, A. Guy; Simmonds, Mark O.; Worth, Gillian H.

doi:10.1039/dt9910001595

Cited by 21 publications

(7 citation statements)

References 18 publications

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“…Unless stated otherwise (i) complexes were purified by dissolution in CH 2 Cl 2 , filtration of the solution through Celite, addition of n-hexane to the filtrate and reduction of the volume of the mixture in vacuo to induce precipitation, and (ii) are stable under nitrogen and dissolve in polar solvents such as CH 2 Cl 2 , acetone and thf to give moderately air-stable solutions. The compounds trans-[Mn(CN)(CO)(dppm) 2 ], 19 [Mn(CN 22 and [Fe(η-C 5 H 5 )(η-C 5 H 4 CO-Me)][PF 6 ] 22 were prepared by published methods. IR spectra were recorded on a Nicolet 5ZDX FT spectrometer and UV-visible spectra on a Perkin-Elmer Lambda 2 UV/VIS spectrometer.…”

Section: Methodsmentioning

confidence: 99%

Coordination chemistry of a bulky redox-active cyanomanganese carbonyl ligand: N-bound tetrahedral complexes of 3d metals

Connelly

Hicks

Lewis

et al. 2000

J. Chem. Soc., Dalton Trans.

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Section: Methodsmentioning

confidence: 99%

Coordination chemistry of a bulky redox-active cyanomanganese carbonyl ligand: N-bound tetrahedral complexes of 3d metals

Connelly

Hicks

Lewis

et al. 2000

J. Chem. Soc., Dalton Trans.

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“…The final form of the Kamlet-Taft expression obtained for 6 3+ is shown in eqn (2), where data for all non-halogenated alcohols (reactive) and aniline (reactive, with poor correlation plots) were excluded from the regression analysis. Equations displaying statistically stronger correlations could be obtained by excluding different solvents, but it was unclear whether such exclusions were judicious or arbitrary.…”

Section: Optical Properties Of Cyanomanganese(i) Pentaammineruthenium...mentioning

confidence: 99%

Metal–metal charge transfer and solvatochromism in cyanomanganese carbonyl complexes of ruthenium and osmium

et al. 2006

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The complexes [(H3N)5Ru(II)(mu-NC)Mn(I)Lx]2+, prepared from [Ru(OH2)(NH3)5]2+ and [Mn(CN)L(x)] {L(x) = trans-(CO)2{P(OPh)3}(dppm); cis-(CO)2(PR3)(dppm), R = OEt or OPh; (PR3)(NO)(eta-C5H4Me), R = Ph or OPh}, undergo two sequential one-electron oxidations, the first at the ruthenium centre to give [(H3N)5Ru(III)(mu-NC)Mn(I)Lx]3+; the osmium(III) analogues [(H3N)5Os(III)(mu-NC)Mn(I)Lx]3+ were prepared directly from [Os(NH3)5(O3SCF3)]2+ and [Mn(CN)Lx]. Cyclic voltammetry and electronic spectroscopy show that the strong solvatochromism of the trications depends on the hydrogen-bond accepting properties of the solvent. Extensive hydrogen bonding is also observed in the crystal structures of [(H3N)5Ru(III)(mu-NC)Mn(I)(PPh3)(NO)(eta-C5H4Me)][PF6]3.2Me2CO.1.5Et2O, [(H3N)5Ru(III)(mu-NC)Mn(I)(CO)(dppm)2-trans][PF6]3.5Me2CO and [(H3N)5Ru(III)(mu-NC)Mn(I)(CO)2{P(OEt)3}(dppm)-trans][PF6]3.4Me2CO, between the amine groups (the H-bond donors) at the Ru(III) site and the oxygen atoms of solvent molecules or the fluorine atoms of the [PF6]- counterions (the H-bond acceptors).

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“…As an extension of previous studies, by us 1 and others, 2 of complexes in which a cyanide ligand bridges two metal-based redox centres, we have recently reported 3 a series of homobinuclear species, [(o-O 2 C 6 Cl 4 )L(OC) 2 Ru(l-CN)Ru(CO) 2 L (o-O 2 C 6 Cl 4 )] − {L or L = PPh 3 or P(OPh) 3 }, in which sequential one-electron oxidation occurs at the two ligand-based (catecholate) centres. We now describe heterobinuclear species in which the ligand-based redox centres Ru(XY)(CO) 2 L(o-O 2 C 6 Cl 4 ) {XY = CN or NC, L = PPh 3 or P(OPh) 3 } are C-or N-bound either to a redox-active Mn(I) centre, as in [(o-O 2 C 6 Cl 4 )(Ph 3 P)(OC) 2 Ru(l-XY)MnL(NO)(g-C 5 Me 5 )] (XY = CN or NC, L = CNBu t or CNXyl), related to previous species such as [(o-O 2 C 6 Cl 4 )(Ph 3 P)(OC) 2 Ru(l-NC)Mn(CO) 2 (PEt 3 )(dppe)-cis], 4 or to an M(alkyne) group, as in [(o-O 2 C 6 Cl 4 )L(OC) 2 Ru(l-XY)M(CO)(PhC≡CPh)Tp ] (M = Mo or W), where redox activity is centred on the metal-alkyne unit. In both series, electrochemical and spectroscopic studies have shed light on the effect of linkage isomerisation and ancillary ligand sets on electron transfer between linked metal-and ligand-based redox centres.…”

Section: Introductionmentioning

confidence: 99%

Cyanide-bridged linkage isomers with catecholateruthenium(ii) centres bound to Mn(i) or M(alkyne) units

2007

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Two series of stable cyanide-bridged linkage isomers, namely [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-XY)MnL(NO)(eta-C5Me5)] (XY = CN or NC, L = CNBu(t) or CNXyl) and [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC-CPh)Tp'] {M = Mo or W, L = PPh3 or P(OPh)3, Tp' = hydrotris(3,5-dimethylpyrazolyl)borate} have been synthesised; pairs of isomers are distinguishable by IR spectroscopy and cyclic voltammetry. The molecular structure of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-NC)Mo(CO)(PhC-CPh)Tp'] has the catecholate-bound ruthenium atom cyanide-bridged to a Mo(CO)(PhC[triple band]CPh)Tp' unit in which the alkyne acts as a four-electron donor; the alignment of the alkyne relative to the Mo-CO vector suggests the fragment (CN)Ru(CO)2(PPh3)(o-O2C6Cl4) acts as a pi-acceptor ligand. The complexes [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-XY)Mn(NO)L(eta-C5Me5)] undergo three sequential one-electron oxidation processes with the first and third assigned to oxidation of the ruthenium-bound o-O2C6Cl4 ligand; the second corresponds to oxidation of Mn(I) to Mn(n). The complexes [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC[triple band]CPh)Tp'] are also first oxidised at the catecholate ligand; the second oxidation, and one-electron reduction, are based on the M(CO)(PhC[triple band]CPh)Tp' fragment. Chemical oxidation of [(o-O,C6Cl4)(Ph3P)(OC)2Ru(mu-XY)MnL(NO)(eta-C5Me5)] with [Fe(eta-C5H4COMe)(eta-C5H5)][BF4], or of [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC[triple band]CPh)Tp'] with AgBF4, gave the paramagnetic monocations [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-XY)MnL(NO)(eta-C5Me5)]+ and [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC[triple band]CPh)Tp']+, the ESR spectra of which are consistent with ruthenium-bound semiquinone ligands. Linkage isomers are distinguishable by the magnitude of the 31P hyperfine coupling constant; complexes with N-bound Ru(o-O2C6Cl4) units also show small hyperfine coupling to the nitrogen atom of the cyanide bridge.

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Reduction-oxidation properties of organo-transition metal complexes. Part 33. Ligand-vs. metal-based oxidation of cyano-bridged catecholatoruthenium–manganese carbonyl compounds: the X-ray crystal structure of cis-[(dppe)(Et₃P)(OC)₂Mn(µ-CN)Ru(CO)₂(PPh₃)(o-O₂C₆Cl₄)]·CH₂Cl₂

Cited by 21 publications

References 18 publications

Coordination chemistry of a bulky redox-active cyanomanganese carbonyl ligand: N-bound tetrahedral complexes of 3d metals

Coordination chemistry of a bulky redox-active cyanomanganese carbonyl ligand: N-bound tetrahedral complexes of 3d metals

Metal–metal charge transfer and solvatochromism in cyanomanganese carbonyl complexes of ruthenium and osmium

Cyanide-bridged linkage isomers with catecholateruthenium(ii) centres bound to Mn(i) or M(alkyne) units

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