Dinuclear RhII-Phthalocyaninates with a Rh-Rh Single Bond: X-ray Crystal Structure of Di(pyridinephthalocyaninato(2-)rhodium(II))

Hückstädt, Heiner; Bruhn, Clemens; Homborg, H.

doi:10.1002/(sici)1099-1409(199710)1:4<367::aid-jpp31>3.0.co;2-q

Cited by 22 publications

(6 citation statements)

References 27 publications

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“…Isolation of single crystals suitable for X-ray work is rare in the case of (ML) 2 complexes, L being a phthalocyanine or porphyrin ligand, and the structure has been solved only for the porphyrin derivatives [(OEP)Ru] 2 4 and [(TPP)Mo] 2 . Very recently, two new phthalocyanine dimers, i.e., (PcIr) 2 and (PcRh) 2 , have been reported, but elucidation of the structure by X-rays has only been achieved on their bis(pyridine) adducts, [PcM(py)] 2 . So far, then, (PcRu) 2 appears to be the only (PcM) 2 species for which detailed structural information has been reported 1b.…”

Section: Introductionmentioning

confidence: 99%

Dimeric Osmium Phthalocyanine Organized in Discrete Columnarly Stacked Assemblies: Structure, Magnetism, and Electrical Conductivity Properties

et al. 1998

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Solid pure osmium phthalocyanine, as obtained from its adduct [PcOs(py)(2)], is an air-stable solid amorphous material. Its structure has been examined by the wide-angle X-ray scattering (WAXS) technique. Experimental data are best fitted by assuming the molecule to consist of a dimeric unit, (PcOs)(2), held together by a direct metal-metal linkage. The short Os-Os distance (2.38(1) Å) is consistent with the presence of a double bond between the two Os(II) atoms. Each Pc skeleton has a domed conformation with displacement of the respective Os atom from the plane of the four coordinating nitrogen atoms (0.40 Å) toward the other Os atom. The solid-state structure consists of disordered couples of parallel chains of (PcOs)(2). On average, six dimeric units are aligned along the stacking direction within each chain. The relative orientation of the two intradimer Pc units is 30 degrees, eclipsing occurring for the interdimer adjacent Pc units along the chain. Magnetic susceptibility measurements in the temperature range 5-300 K indicate a strong spin-spin coupling for the two metal centers in the dimer and suggest an electronic energy level sequence sigma(2)pi(4)delta(2)delta(2)pi(2) and a nonmagnetic ground state for the complex. Room-temperature electrical conductivity measurements show a sigma(RT) value of 1 x 10(-)(5) Omega(-)(1) cm(-)(1).

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Section: Introductionmentioning

confidence: 99%

Dimeric Osmium Phthalocyanine Organized in Discrete Columnarly Stacked Assemblies: Structure, Magnetism, and Electrical Conductivity Properties

et al. 1998

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“…[Rh 2 (EtCN) 10 ] 4+ has the shortest distance of 2.604 (1) Å among the reported structures. Repulsion between the equatorial ligands made the Rh-Rh distance longer, as observed in [Rh 2 (dmg) 4 (py) 2 ] (Hdmg = dimethylglyoxime; Kuz'menko et al, 1991) or [Rh 2 (pc) 2 (py) 2 ] (H 2 pc = phthalocyanine; Huckstadt et al, 1997). A strong donor axial ligand also changed the distance that is observed between [Rh 2 (dmg) 4 (PPh 3 ) 2 ] (Caulton & Cotton, 1971) and [Rh 2 (dmg) 4 (py) 2 ].…”

Section: Complexesmentioning

confidence: 86%

“…Rh-Rh (Å ) Reference (Caulton & Cotton, 1971;Dikareva et al, 1989;Dunbar, 1988;Huckstadt et al, 1997;Inoki et al, 2012;Kuz'menko et al, 1991;Li et al, 2013;Olmstead & Balch, 1978;Prater et al, 1999). [Rh 2 (EtCN) 10 ] 4+ has the shortest distance of 2.604 (1) Å among the reported structures.…”

Section: Complexesmentioning

confidence: 99%

Assembled structures of tetrakis(biimidazole)dirhodium complexes hydrogen-bonded with common inorganic anions

Jinlong

Uemura

Ebihara

2014

Acta Crystallogr Sect B

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Eight new structures of dirhodium complexes, each with four biimidazole (H2bim) ligands, were obtained: [Rh2(H2bim)4(H2O)2](NO3)4·4H2O (I), [Rh2(H2bim)4(H2O)2](ClO4)4·5H2O (II), [Rh2(H2bim)4(MeOH)2](ClO4)4 (III), [Rh2(H2bim)4(DMF)2](BF4)4 (IV), [Rh2(H2bim)4(Mepy)2](SiF6)2·8H2O (V), [{Rh2(H2bim)4(pz)}2(μ-pz)](SiF6)(ClO4)6·12.7H2O (VI), [{Rh2(H2bim)4(pz)}2(μ-pz)](ClO4)8·11.4H2O (VII) and [Rh2(H2bim)4(μ-pz)](SiF6)2·6H2O (VIII). The unbridged Rh-Rh bond distances range between 2.6313 (8) and 2.7052 (5) Å. The dirhodium units adopt a staggered conformation with torsion angles N-Rh-Rh-N of 37.6 (4)-48.98 (8)°. Various assembled structures were constructed by hydrogen bonding between the complexes and the anions: a discrete structure in (IV), one-dimensional structure in (II), two-dimensional structures in (I), (III), (VI), (VII) and (VIII) and a three-dimensional structure in (V).

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“…Therefore, the two (RPc)Rh macrocycles of 7a are either exactly eclipsed or exactly 45°-staggered. However, the exactly eclipsed isomer can be ruled out if we assume that the Rh−Rh bond length of 7 is close to that of [(Pc)(py)Rh] 2 , i.e., 2.74 Å . Such a short distance between the two (RPc)Rh macrocycles results in repulsion between the π-electrons of the two (RPc)Rh macrocycles and precludes the formation of the exactly eclipsed isomer.…”

Section: Discussionmentioning

confidence: 99%

Paramagnetic Rh(III) Complexes from Reactions of Phosphines with Hydride-Bridged and Nonbridged Rhodium Phthalocyanine Dimers: Metal-to-Ligand Charge Transfer Induced by Phosphines

1998

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The paramagnetic rhodium phthalocyanine complex (RPc)(PMe3)2Rh (4) (RPc = dianion of 1,4,8,11,15,18,22,25-octa-n-pentylphthalocyanine) has been prepared by the reaction of trimethylphosphine (PMe3) with hydride-bridged and nonbridged rhodium phthalocyanine dimers. The reaction of the μ-hydrido complex (RPcH)Rh(μ-H)Rh(RPc) (5) (RPcH = RPc with one of its meso nitrogens protonated) with PMe3 at −10 °C produces (RPc)(PMe3)RhH (6), which further reacts with PMe3 to produce 4 and H2 at higher temperatures. If the solution of 6 is allowed to warm in the absence of free PMe3, H2 is also liberated and 6 is converted to an equal number of moles of 4 and [(RPc)Rh]2(PMe3) (7). In contrast, the reaction of 5 with pyridine (py) produces (RPc)(py)RhH (11), which does not react with additional pyridine. Alternatively, 4 is generated by the reaction of the Rh−Rh bonded dimer [(RPc)Rh]2 (1) with PMe3. In this reaction, the formation of 7 as an intermediate may be shown by the titration of 1 with PMe3. Complex 1 reacts with 4 to produce (RPc)Rh- (10) and (RPc)(PMe3)2Rh+ (9). A redox exchange between 4 and 9 ensues. The cobalt analogue of 4, i.e., (RPc)(PMe3)2Co (12), was generated reversibly by the reaction of (RPc)Co (13) with PMe3 at low temperatures. The 1H NMR and the ESR spectra of 4, 12, and 13 indicate that while 13 is a metal-centered radical, 4 and 12 are best described as ligand-centered radicals. Therefore, 4 and 12 are formulated as Rh(III) and Co(III) complexes of the singly reduced π-radical anion RPc•-, generated by metal-to-ligand charge-transfer reactions induced by phosphines. Consistent with formulation of 4 as a Rh(III) complex, it is only slowly oxidized in air and its PMe3 ligand is slow to exchange with the free phosphine.

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Dinuclear Rh^II-Phthalocyaninates with a Rh-Rh Single Bond: X-ray Crystal Structure of Di(pyridinephthalocyaninato(2-)rhodium(II))

Cited by 22 publications

References 27 publications

Dimeric Osmium Phthalocyanine Organized in Discrete Columnarly Stacked Assemblies: Structure, Magnetism, and Electrical Conductivity Properties

Dimeric Osmium Phthalocyanine Organized in Discrete Columnarly Stacked Assemblies: Structure, Magnetism, and Electrical Conductivity Properties

Assembled structures of tetrakis(biimidazole)dirhodium complexes hydrogen-bonded with common inorganic anions

Paramagnetic Rh(III) Complexes from Reactions of Phosphines with Hydride-Bridged and Nonbridged Rhodium Phthalocyanine Dimers: Metal-to-Ligand Charge Transfer Induced by Phosphines

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