ChemInform Abstract: RHODIUM THIOACETATE COMPLEXES

Baranovskii, I. B.; Golubnichaya, M. A.; Mazo, G. Ya.; Nefedov, V. I.; Salyn, Ya. V.; Shchelokov, R.N.

doi:10.1002/chin.197629317

Cited by 4 publications

(4 citation statements)

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“…Crystallographic Studies.-Each of the compounds characterised by X-ray crystallography in this study (Figures 1-3 The structural distinction between axial and equatorial MeCN ligands does not extend to their N-C and C-C bond lengths; the overall average lengths of these bonds are 1.13 (2) and 1.44(3) A, respectively, and are normal for MeCN molecules complexed to other metal Also, as generally observed 3*9-11 for other complexes of Mo2,+ centres with monodentate ligands, the equatorial MeCN groups make an obtuse angle with the Mo-Mo bond, Mo-Mo-N,, 102(3)".…”

Section: Resultsmentioning

confidence: 90%

Synthesis, crystal structure, and spectroscopic properties of [Mo2(O2CMe)2(MeCN)6][BF4]2, [Rh2(O2CMe)2(MeCN)6][BF4]2, and [Rh2(O2CMe)2(MeCN)4(py)2][BF4]2

Pimblett¹,

Garner²,

Clegg³

1986

J. Chem. Soc., Dalton Trans.

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Section: Resultsmentioning

confidence: 90%

Synthesis, crystal structure, and spectroscopic properties of [Mo2(O2CMe)2(MeCN)6][BF4]2, [Rh2(O2CMe)2(MeCN)6][BF4]2, and [Rh2(O2CMe)2(MeCN)4(py)2][BF4]2

Pimblett¹,

Garner²,

Clegg³

1986

J. Chem. Soc., Dalton Trans.

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“…Rh 2 (NCCH 3 ) 8 (NCH) 2 4+ . This species is a close congener to Rh 2 (NCCH 3 ) 10 4+ , which has been subjected to crystallographic characterization in several forms. − The substitution of the two terminal acetonitrile ligands by HCN in our calculations was undertaken so as to permit calculation in C 4 v symmetry, at substantially reduced computational cost, in contrast to the requirement for C s symmetry imposed by retaining terminal CH 3 CN. It is likely that coulombic distortion, rather than our virtual ligand-switching, is responsible for the systematic overestimation of the Rh−Rh bond length in our calculations, although it is also worth commenting that the two rhodium-containing complexes studied in the present work (one neutral, one quadruply charged) are the only two species for which all DFT methods, including VWN and VWN+B-LYP, yield results which lie above the upper limit of the target range.…”

Section: Resultsmentioning

confidence: 99%

DFT and Metal−Metal Bonding: A Dys-Functional Treatment for Multiply Charged Complexes?

Petrie

Stranger

2004

Inorg. Chem.

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Density functional theory (DFT) calculations are reported for 16 binuclear transition-metal complexes. Structural motifs studied include face-shared and edge-shared bioctahedra, carboxylate-bridged "paddlewheel" complexes, and nonbridged dimers possessing direct metal-metal bonds. Most of these structure types are represented both by multiply charged (tri- and tetra-anionic, and tetracationic) and by neutral or singly charged examples. Geometry optimizations for these species, in the vacuum phase, use the "broken-symmetry" approach coupled with nine different DFT methods. We find a clear dichotomy in the performance of different DFT approaches. For the eight neutral or singly charged complexes, orthodox gradient-corrected DFT methods such as BP and PBE perform generally very well in reproducing in vacuo the complex geometries obtained from X-ray crystallographic studies. In contrast, these orthodox approaches fail to reliably mimic the crystalline geometries for more highly charged complexes such as Mo(2)Cl(9)(3-), Cr(2)(CH(3))(8)(4-), and Rh(2)(NCCH(3))(10)(4+). Much closer agreement with experimental condensed-phase structures for the multiply charged dinuclear complexes is seen for two "local-density-approximation" approaches, X alpha and VWN, and for VWN+B-LYP, an unorthodox combination of the VWN local and B-LYP nonlocal density functionals. The very good performance of the latter approaches arises from an essentially fortuitous cancellation of errors: while the generally overbinding nature of these approaches suggests that they will not reliably describe true gas-phase structures, this overbinding compensates very well for the coulombic distortion expected when complexes are removed from the charge-stabilizing environment of the crystalline or solvated state. We recommend that, as an alternative to the (computationally expensive) incorporation of solvent-field corrections, VWN+B-LYP is the preferred method for structural characterization of triply or more highly charged dinuclear complexes, while orthodox approaches such as PBE perform best for neutral or mildly charged complexes.

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“… Dirhodium(II,II) complexes containing O , O' ‐bridging ligands with structural motive OOCAr: P1 , [182] P2 , [198] P3 , [24] P4 R'=Me, [199] P4 R'=C 9 H 19 , R'=C 13 H 27 , [200] P5 , [39] P6 , [201] P6‐2 (Cl), [202] P6‐2 (F), [203] P7 , [182] P8 , [204] P9 , [17] P10 , [205] P11 , [206] P12 , [207] P13 , [208] P14 , [208] P15 , [208] P16 , [209] P17 , [194] P18 , [210] P19 , [211] P20 , [212] P21 , [213] P22, [213] P23 , [213] P24 , [214] P25 , [215] P26 , [273] P27 [273] …”

Section: Overview Of Rh2a4 Paddlewheel Complexesmentioning

confidence: 99%

Dirhodium(II,II) Paddlewheel Complexes

Hrdina

2021

Eur J Inorg Chem

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This minireview summarizes synthetic approaches towards homoleptic dirhodium(II,II) paddlewheel complexes with the general formula Rh2A4. These complexes have found numerous applications in a wide range of chemical research and industry as catalysts, detectors, enzymatic inhibitors or building blocks for molecular scaffolds. In organic synthesis they are commonly used to transfer electron‐deficient species, they act as Lewis acids to activate unsaturated bonds, serve as hydrogenation catalysts and participate in oxidation/reduction processes. Dirhodium paddlewheel complexes are composed of the Rh‐Rh backbone and four bridging anions, which surround the core. According to the application, the electrochemical potential of the Rh atom can be modulated, as can the geometry and physical and chemical properties of the metal complex. Dirhodium complexes can be prepared in one step from basic inorganic precursors or by post‐functionalization of the paddlewheel structures.

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ChemInform Abstract: RHODIUM THIOACETATE COMPLEXES

Abstract: Durch Erwärmen von Rh2(HCOO)4°C H2O mit einem Überschuß von Thioessigsäure läßt sich das Thioacetat (Ia) darstellen.

Cited by 4 publications

References 0 publications

Synthesis, crystal structure, and spectroscopic properties of [Mo2(O2CMe)2(MeCN)6][BF4]2, [Rh2(O2CMe)2(MeCN)6][BF4]2, and [Rh2(O2CMe)2(MeCN)4(py)2][BF4]2

Synthesis, crystal structure, and spectroscopic properties of [Mo2(O2CMe)2(MeCN)6][BF4]2, [Rh2(O2CMe)2(MeCN)6][BF4]2, and [Rh2(O2CMe)2(MeCN)4(py)2][BF4]2

DFT and Metal−Metal Bonding: A Dys-Functional Treatment for Multiply Charged Complexes?

Dirhodium(II,II) Paddlewheel Complexes

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