The structure of trimethylphenylammonium nonachlorodirhodate(III) and a survey of metal-metal interactions in confacial bioctahedra

Cotton, F. Albert; Ucko, David A.

doi:10.1016/s0020-1693(00)91778-x

Cited by 102 publications

(68 citation statements)

References 20 publications

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“…Face-sharing biooctahedral complexes of the type L 3 M(m-X) 3 ML 3 form a large and well-studied group of molecules. [56][57][58] However, to our knowledge there are no examples of complexes in which two iron atoms share one O and two S bridging atoms. The Fe 2 (RS) 2 (O) core also reveals a striking asymmetry in the Fe II À OH bond lengths.…”

Section: Resultsmentioning

confidence: 97%

Mononuclear, Dinuclear, and Pentanuclear [{N,S(thiolate)}Iron(II)] Complexes: Nuclearity Control, Incorporation of Hydroxide Bridging Ligands, and Magnetic Behavior

Krishnamurthy

Sarjeant

Goldberg

et al. 2005

Chemistry A European J

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The mixed N3S(thiolate) ligand 1-[bis[2-(pyridin-2-yl)ethyl]amino]-2-methylpropane-2-thiol (Py2SH) was used in the synthesis of four iron(II) complexes: [(Py2S)FeCl] (1), [(Py2S)FeBr] (2), [(Py2S)4Fe5II(mu-OH)2](BF4)4 (3), and [(Py2S)2Fe2II(mu-OH)]BF4 (4). The X-ray structures of 1 and 2 revealed monomeric iron(II)-alkylthiolate complexes with distorted trigonal-bipyramidal geometries. The paramagnetic 1H NMR spectra of 1 and 2 display resonances from delta = -25 ppm to +100 ppm, consistent with a high-spin iron(II) ion (S = 2). Spectral assignments were made on the basis of chemical shift information and T1 measurements and show the monomeric structures are intact in solution. To provide entry into hydroxide-containing complexes, a novel synthetic method was developed involving strict aprotic conditions and limiting amounts of H2O. Reaction of Py2SH with NaH and Fe(BF4)2.6 H2O under aprotic conditions led to the isolation of the pentanuclear, mu-OH complex 3, which has a novel dimer-of-dimers type structure connected by a central iron atom. Conductivity data on 3 show this structure is retained in CH2Cl2. Rational modification of the ligand-to-metal ratio allows control over the nuclearity of the product, yielding the dinuclear complex 4. The X-ray structure of 4 reveals an unprecedented face-sharing, biooctahedral complex with an [S2O] bridging arrangement. The magnetic properties of 3 and 4 in the range 1.9-300 K were successfully modeled. Dinuclear 4 is antiferromagnetically coupled [J = -18.8(2) cm(-1)]. Pentanuclear 3 exhibits ferrimagnetic behavior, with a high-spin ground state of S(T) = 6, and was best modeled with three different exchange parameters [J = -15.3(2), J' = -24.7(3), and J'' = -5.36(7) cm(-1)]. DFT calculations provided good support for the interpretation of the magnetic properties.

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Section: Resultsmentioning

confidence: 97%

Mononuclear, Dinuclear, and Pentanuclear [{N,S(thiolate)}Iron(II)] Complexes: Nuclearity Control, Incorporation of Hydroxide Bridging Ligands, and Magnetic Behavior

Krishnamurthy

Sarjeant

Goldberg

et al. 2005

Chemistry A European J

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“…Although the octahedral distortion found in the title compound is quite significant, it is not the first example of such large differences in Rh-Clbond lengths. Asimilar situation with even larger Rh-Cl deviation (0.035(3) Å) within the sameoctahedron was found in the structure of bis(1,2-diammoniopropane) hexachloridorhodate(III) chloride [3], whereas the largest linear distortion (difference in Rh-Cl bond lengths of 0.215(16) Å) was reported for the [Rh 2 Cl 9 ] 3-dinuclear anion in the structure of trimethylphenylammonium nonachloridodirhodate(III) [6]. …”

Section: Methodsmentioning

confidence: 68%

Crystal structure of the inorganic-organic hybrid material bis(N,Ndimethyl- 1,3-diammoniopropane) hexachloridorhodate(III) chloride, [(CH3)2NH(CH2)3NH3]2[RhCl6]Cl, C10H32Cl7N4Rh

Bujak

Frank

2014

Zeitschrift Für Kristallographie - New Crystal Structures

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“…An interesting comparison can be made between the pair Mo2X3s -(X=CI, Br) on the one hand and the pair Mo2X93-(X=C1,Br) (Saillant et al, 1971) on the other. Both of the nonahalo anions have much longer Mo-Mo distances (2.66, 2.82,~) than their octahalo analogs (2.38, 2.44 A), and according to all criteria (Cotton & Ucko, 1972) have markedly weaker Mo-Mo bonding interactions. The metal-to-halogen bonds in the two sets of compounds are presumably very similar since corresponding bond distances differ very little, except for the Mo-Br(bridge) bond distances.…”

Section: Discussionmentioning

confidence: 94%

“…According to all the criteria previously proposed (Cotton & Ucko, 1972) for evaluating the nature and magnitude of the direct metal-to-metal interaction in confacial bioctahedra, the Mo-Mo interaction is unquestionably of a bonding nature, but slightly less strong than that in Mo2CI~-. Thus in Mo2C18 a-the Mo-Mo distance is 2.38 (1)~, while in Mo2Br 3-it is 2.439 (7) A.…”

Section: Discussionmentioning

confidence: 99%

The structure of tricesium octabromodimolybdate: an example of a space-group ambiguity

Cotton¹,

Frenz²,

Mester³

1973

Acta Crystallogr Sect B

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When tetraacetatodimolybdenum is dissolved in aqueous hydrobromic acid and a solution of CsBr is added, a precipitate of microcrystalline CssMozBr8 is formed. By a special technique, crystallographically useful single crystals were obtained and the substance has been structurally characterized. The structure consists of Cs + cations and MozBr 3-anions, the latter having the shape of an MzX9 confacial bioctahedron but with crystallographically disordered vacancies in the bridging positions. The dimensions of the Mo2Br~-ion indicate that there is bonding interaction of medium strength between the molybdenum atoms. The crystals belong to the hexagonal system, with space groups P~2c, P63/mmc and P63mc admissible on the basis of systematic absences. P6smc was eliminated convincingly on the basis of unsatisfactory refinement, but no clear choice between the other two space groups was possible using diffraction data. The unit-cellj~parameters are a= 7.757 (3), c= 17.804 (7)A, Z= 2; dcale =4"40; doh~=4"33 g cm -3. The Mo-Mo distance is 2.439 (7); Mo-Br(terminal)=2.554 (3); Mo-Br(bridge)= 2.672 (5) A.

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The structure of trimethylphenylammonium nonachlorodirhodate(III) and a survey of metal-metal interactions in confacial bioctahedra

Cited by 102 publications

References 20 publications

Mononuclear, Dinuclear, and Pentanuclear [{N,S(thiolate)}Iron(II)] Complexes: Nuclearity Control, Incorporation of Hydroxide Bridging Ligands, and Magnetic Behavior

Mononuclear, Dinuclear, and Pentanuclear [{N,S(thiolate)}Iron(II)] Complexes: Nuclearity Control, Incorporation of Hydroxide Bridging Ligands, and Magnetic Behavior

Crystal structure of the inorganic-organic hybrid material bis(N,Ndimethyl- 1,3-diammoniopropane) hexachloridorhodate(III) chloride, [(CH3)2NH(CH2)3NH3]2[RhCl6]Cl, C10H32Cl7N4Rh

The structure of tricesium octabromodimolybdate: an example of a space-group ambiguity

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