The crystal and molecular structure of sodium hexacyanoosmate(II) decahydrate and related hexacyanometalate complexes

Gentil, Luis A.; Navaza, A.; Olabe, José A.; Rigotti, G.

doi:10.1016/s0020-1693(00)85378-5

Cited by 24 publications

(16 citation statements)

References 20 publications

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“…23 Nevertheless, crystallographic measurements [22][23][24][25][26][27][28][29][30][31] indicate ∆d 0 ) 4 pm for the Mo(CN) 8 3-/4and W(CN) 8 3-/4couples, and Macartney 11 argues for a similar ∆d 0 for Os(CN) 6 3-/4-, so that, in contrast to the Fe(CN) 6 3-/4case, where ∆d 0 is zero, a small, positive, "intrinsic" (i.e., molecular volume change) contribution to ∆V Ag/AgCl may be expected to accompany reduction in these couples and to increase with increasing d 0 . For Fe(CN) 6 4-, Os(CN) 6 4-, Mo(CN) 8 4-, and W(CN) 8 4-, d 0 in solids is typically 193, 204, 216, and 218 pm, respectively, [23][24][25][26][27][28][29][30][31] and so the trend Fe < Os < Mo < W in ∆V Ag/AgCl may be qualitatively understood. Corresponding increases in the overall effective radii r of the reactants will also make minor contributions to this trend through eq 6.…”

Section: Discussionmentioning

confidence: 99%

Electrochemical Kinetics of Cyanometalate Complexes in Aqueous Solution at High Pressures

Swaddle

1999

Inorg. Chem.

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For the aqueous couples Os(CN)(6)(3-/4-), Mo(CN)(8)(3-/4-), and W(CN)(8)(3-/4-), volumes of reaction DeltaV(Ag/AgCl) relative to Ag/AgCl/4.0 mol L(-)(1) KCl and volumes of activation DeltaV(el)() for the electrode reactions are reported. Values of DeltaV(Ag/AgCl) are consistent with a very small increase in the metal-carbon bond length on reduction in each case, the main component of DeltaV(Ag/AgCl) (other than that of the reference electrode) being electrostrictive solvation change. For media in which the cation is 0.5 mol L(-)(1) K(+) or (for Mo) Na(+), DeltaV(el)() is strongly positive (+9.4 +/- 0.7, +7.3 +/- 0.7, and +10.8 +/- 0.4 cm(3) mol(-)(1) for Os(CN)(6)(3-/4-), Mo(CN)(8)(3-/4-), and W(CN)(8)(3-/4-), respectively, at 25 degrees C), whereas the theoretical expectation for a mechanism involving only the cyanometalate anions is -3 +/- 1 cm(3) mol(-1). For Mo(CN)(8)(3-/4-) in Et(4)NCl, however, DeltaV(el)() is -4.2 +/- 0.2 cm(3) mol(-)(1). In all cases, DeltaV(el)() is just one-half of the corresponding parameter DeltaV(ex)() for the homogeneous (bimolecular) self-exchange reaction of the same couple, giving strong confirmation of the "fifty-percent rule" (Fu, Y.; Swaddle, T. W. J. Am. Chem. Soc. 1997, 119, 7137). These and related results are interpreted in terms of a mechanism for both electrode and homogeneous electron-transfer reactions of cyanometalates in which the counterion mediates the electron-transfer process. For alkali metal cations, partial deaquation to permit this mediation results in positive DeltaV(el)() values, whereas for tetraalkylammonium counterions, there are no aqua ligands to be removed and DeltaV(el)() is "normal".

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Section: Discussionmentioning

confidence: 99%

Electrochemical Kinetics of Cyanometalate Complexes in Aqueous Solution at High Pressures

Swaddle

1999

Inorg. Chem.

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“…The complexes K 4 [Ru(CN) 6 ], 10 K 4 [Os(CN) 6 ], 11 (TPP) 3 [Os(CN) 6 ], 12 [Ru( py) 4 (CN) 2 ], 13 [Ru(tpm)(bpy)Cl]Cl, 14 [Ru(tpm)(bpy)(OH 2 )]-(PF 6 ) 2 , 14 [Ru(tpy)(bpy)Cl]Cl, 15 and [Ru(tpy)(bpy)(OH 2 )](PF 6 ) 2 were prepared as described in previous reports (TPP + = tetraphenylphosphonium). All other reagents were obtained commercially and used without further purification.…”

Section: Methodsmentioning

confidence: 99%

Emissive cyanide-bridged bimetallic compounds as building blocks for polymeric antennae

et al. 2013

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A series of cyanide-bridged bimetallic compounds of the general formula [Ru(L)(bpy)(μ-NC)(M)](2-/-/2+) (L = tpy, 2,2'-6',2''-terpyridine, or tpm, tris(1-pyrazolyl)methane, bpy = 2,2'-bipyridine, M = Ru(II)(CN)5, Os(III)(CN)5, Os(II)(CN)5, Ru(II)(py)4(CN), py = pyridine) have been synthesized and fully characterized. Most of them present MLCT emission (λ = 690-730 nm, Φ = 10(-3)-10(-4)) and their photophysical properties resemble the ones of the respective mononuclear Ru(L)(bpy) species. The exception is when M is Os(III)(CN)5, where an intramolecular electron transfer quenching mechanism is proposed. The conditions that should be met for avoiding the reductive or oxidative quenching of the excited state are also discussed.

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“…26 SMM behavior has been reported for compounds based on the Re II , 4 Re IV , 26 and W V 27 precursors.Given the success with Group 6 and 7 transition elements, we have extended our exploration of cyanometallate anion chemistry to the Group 8 analog [Os III (CN) 6 ] 3À . Although it has been known in the literature for some time, [28][29][30] this anion was only recently structurally characterized as the tetraphenylarsonium salt, [Ph 4 As] 3 [Os III (CN) 6 ], 28 and the magnetic properties determined. Herein we report the synthesis and magnetic properties of a trigonal bipyramidal (TBP) cluster and a Prussian blue phase of Os III in combination with Ni II ions, the first cyanide-bridged materials based on the hexacyanoosmate(III) anion.…”

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confidence: 99%

Hexacyanoosmate(iii) chemistry: preparation and magnetic properties of a pentanuclear cluster and a Prussian blue analogue with Ni(ii)

et al. 2008

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The crystal and molecular structure of sodium hexacyanoosmate(II) decahydrate and related hexacyanometalate complexes

Cited by 24 publications

References 20 publications

Electrochemical Kinetics of Cyanometalate Complexes in Aqueous Solution at High Pressures

Electrochemical Kinetics of Cyanometalate Complexes in Aqueous Solution at High Pressures

Emissive cyanide-bridged bimetallic compounds as building blocks for polymeric antennae

Hexacyanoosmate(iii) chemistry: preparation and magnetic properties of a pentanuclear cluster and a Prussian blue analogue with Ni(ii)

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