Rhodium and iridium complexes of biimidazole.  2.  Tetranuclear carbonyl derivatives

Kaiser, Sabine; Saillant, R. B.; Butler, William M.; Rasmussen, Paul G.

doi:10.1021/ic50165a024

Cited by 59 publications

(13 citation statements)

References 6 publications

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“…The data for selected AsF;, AuF6-, 11,14,[16][17][18][19][20] Table VI, shows the pattern. In general, the CsCl type structure occurs only when at least one of the ions is highly polarizable.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of fluoroxenon(1+) hexafluoroarsenate(1-)

Zalkin¹,

Ward²,

Biagioni³

et al. 1978

Inorg. Chem.

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Crystals of XeF+AsF6-are monoclinic, space group P 2 , / n , a = 6.308 (3) A, b = 6.275 (3) A, c = 16.023 (5) A, p = 99.97 (5)', I/ = 624.66 A3, Z = 4, and d, = 3.61 g ~m -~, at 24 'C. X-ray diffraction data were measured with counter methods and Mo Ka radiation. With anisotropic temperature factors for all atoms, R = 0.033 for 777 independent reflections ( I > 36). The structure consists of ion pairs connected by a bridging fluorine atom into FXeFAsF5 units. The FXeF portion of the molecule is linear (angle = 178.9 (7)') with Xe-F = 1.873 (6) A (terminal) and 2.212 (5) 8, (bridging). The FAsF5 portion of the molecule is roughly octahedral with cis F-As-F angles ranging from 85.3 (3) to 94.6 (5)'; the five terminal As-F distances range from 1.676 (5) to 1.690 (8) 8, and the bridging As-F distance is 1.813 (6) A. The bridge Xe-F-As angle is 134.8 (2)'.

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Section: Discussionmentioning

confidence: 99%

Crystal structure of fluoroxenon(1+) hexafluoroarsenate(1-)

Zalkin¹,

Ward²,

Biagioni³

et al. 1978

Inorg. Chem.

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“…It warrants mentioning that shorter distances ranging from 2.612 to 2.841 Å have been found in binuclear Rh(I) complexes with CO or 1,1-bis(diphenylphosphino)methane ligands. 17 Separations of 2.916, 18 2.975, 19 and 2.982 Å 20 have also been observed for related Rh(I)−Rh(I) complexes, where a metal−metal interaction has also been postulated.…”

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confidence: 87%

Amidate-Ligated Complexes of Rhodium(I): A Showcase of Coordination Flexibility

2015

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Reaction of the amidate ligand salts Na[N(Dipp)C(O)R] (R = Ph (1a), tBu (1b); Dipp = 2,6-diisopropylphenyl) with [Rh(NBD)-Cl] 2 (NBD = norbornadiene) proceeds to give the dirhodium(I) complexes [Rh 2 {μ 2 -N,O-N(Dipp)C(O)R} 2 (NBD) 2 ] (R = Ph (2a), tBu (2b)) with variable coordination behavior. For complex 2b, a monomer− dimer equilibrium with the mononuclear complex [Rh{κ 2 -N,O-N(Dipp)-C(O)tBu}(NBD)] (3b) was established for the first time. Precursors 2a,b were treated with PPh 3 and PCy 3 , giving the distorted-square-planar κ 2 -N,O amidates [Rh{κ 2 -N,O-N(Dipp)C(O)R}(PPh 3 ) 2 ] (R = Ph (4a), tBu (4b)) or the κ 1 -O complexes [Rh{κ 1 -O-N(Dipp)C(O)R}(NBD)(PCy 3 )] (R = Ph (5a), tBu (5b)). Initial reactivity screening showed that complex 4b undergoes O 2 activation, providing Ph 3 PO; via the transient peroxo complex 6b, which was characterized in the solution phase. The κ 2 -N,O amidate coordination in 6b has been conclusively established by diagnostic 13 C{ 1 H} NMR spectroscopy.

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“…0.5 V) than the anodic responses for the mononuclear complex. This is due 24 to the stronger π-donor ability of the dianion bridge biim 2Ϫ than the neutral terminal H 2 biim. The separation between two successive anodic responses for the unsymmetrical [(bpy) 2 Ru(biim)Ru(pap) 2 ] 2ϩ is 0.26 V. The first oxidation process, in this case, is assigned to the (bpy) 2 Ru III (biim)-(bpy) 2 Ru II (biim) couple.…”

Section: Electrochemistrymentioning

confidence: 99%

Biimidazole complexes of ML22+ [M = Ru or Os, L = 2-(phenylazo)pyridine]. Synthesis, structure and redox properties of mono- and di-nuclear complexes ‡

Majumdar¹,

Peng²,

Goswami³

1998

J. Chem. Soc., Dalton Trans.

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A series of mono-and di-nuclear complexes of ruthenium and osmium containing the terminal ligands 2-(phenylazo)pyridine (pap), 2,2Ј-bipyridine (bpy) and the bridging ligand 2,2Ј-biimidazole(H 2 biim) have been prepared. The mononuclear complex [Ru(pap) 2 (H 2 biim)][ClO 4 ] 2 ؒ3CH 2 Cl 2 was characterised by a single-crystal structure determination. The mononuclear complexes [M(pap) 2 (H 2 biim)] 2ϩ (M = Ru or Os) act as dibasic acids and undergo deprotonation to afford [M(pap) 2 (Hbiim)] ϩ and [M(pap) 2 (biim)]. The completely deprotonated complexes behave as reactive building units ('metal complex as ligand') which react smoothly with metal complex units to produce homo-and hetero-dinuclear complexes. The structure of the dinuclear complex [Ru 2 (bpy) 4 (biim)][ClO 4 ] 2 was determined. Cyclic voltammetric studies on the above complexes were performed. The quasi-reversible half-wave potentials of the oxidation processes of the dinuclear complexes are dependent on the metal as well as on the nature of the terminal ligands. These undergo two one-electron oxidation processes centered at the metal. Partial oxidation of the dinuclear complexes led to unsymmetrical bridge cleavage to form monomeric complexes. Large numbers of ligand reduction responses were observed. In some cases the first ligand reduction occurs close to zero potential (with respect to the SCE).

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Rhodium and iridium complexes of biimidazole. 2. Tetranuclear carbonyl derivatives

Cited by 59 publications

References 6 publications

Crystal structure of fluoroxenon(1+) hexafluoroarsenate(1-)

Crystal structure of fluoroxenon(1+) hexafluoroarsenate(1-)

Amidate-Ligated Complexes of Rhodium(I): A Showcase of Coordination Flexibility

Biimidazole complexes of ML22+ [M = Ru or Os, L = 2-(phenylazo)pyridine]. Synthesis, structure and redox properties of mono- and di-nuclear complexes ‡

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