| 词条 | Rhodium carbonyl chloride |
| 释义 |
| ImageFile1 = Rh2Cl2(CO)4.svg | ImageSize1 = | ImageFile2 =Rh2Cl2(CO)4.jpg | ImageSize2 = | ImageAlt = | IUPACName = Di-μ-chloro-tetracarbonyldirhodium(I) | OtherNames = Rhodium carbonyl chloride(I), Rhodium(I) carbonyl chloride, Rhodium(I) dicarbonyl chloride dimer, Tetracarbonyldi-μ−chlorodirhodium(I), Dirhodium tetracarbonyl dichloride |Section1={{Chembox Identifiers | CASNo = 14523-22-9 | PubChem = 24852228 | SMILES = }} |Section2={{Chembox Properties | Formula = C4O4Cl2Rh2 | MolarMass = 388.76 | Appearance = red brown volatile solid | Density = 2.708 g/cm−3 | MeltingPt = 120-125 °C | BoilingPt = | Solubility = }} |Section3={{Chembox Hazards | MainHazards = | FlashPt = | AutoignitionPt = }} }} Rhodium carbonyl chloride is an organorhodium compound with the formula Rh2Cl2(CO)4. It is a red-brown volatile solid that is soluble in nonpolar organic solvents. It is a precursor to other rhodium carbonyl complexes, some of which are useful in homogeneous catalysis. StructureThe molecule consists of two planar Rh(I) centers linked by two bridging chloride ligands and four CO ligands. X-ray crystallography shows that the two Rh(I) centers are square planar with the dihedral angle of 53° between the two RhCl2 planes. The metals are nonbonding.[1] Synthesis and reactionsFirst prepared by Walter Hieber,[2] it is typically prepared by treating hydrated rhodium trichloride with flowing carbon monoxide, according to this idealized redox equation: 2 RhCl3(H2O)3 + 6 CO → Rh2Cl2(CO)4 + 2 COCl2 + 6 H2O.[3] The complex reacts with triphenylphosphine to give the bis(triphenylphosphine)rhodium carbonyl chloride: Rh2Cl2(CO)4 + 4 PPh3 → 2 trans-RhCl(CO)(PPh3)2 + 2 CO With chloride salts, the dichloride anion forms: Rh2Cl2(CO)4 + 2 Cl− → 2 cis-[RhCl2(CO)2]− With acetylacetone, rhodium carbonyl chloride reacts to give dicarbonyl(acetylacetonato)rhodium(I). N-heterocyclic carbene (NHC) ligands react with rhodium carbonyl chloride to give monomeric cis-[RhCl(NHC)(CO)2] complexes. The IR spectra of these complexes have been used to estimate the donor strength of NHCs.[4][5]References1. ^Walz, Leonhard; Scheer, Peter "Structure of di-μ-chlorobis[dicarbonylrhodium(I)]" Acta Crystallographica Section C 1991, C47, 640-41. {{DOI|10.1107/S0108270190009404}} {{Rhodium compounds}}2. ^Hieber, W.; Lagally, H. "Über Metallcarbonyle. XLV. Das Rhodium im System der Metallcarbonyle (Metal carbonyls. XLV. Rhodium in the system of metal carbonyls)" Zeitschrift für Anorganische und Allgemeine Chemie 1943, volume 251, pp. 96-113. {{DOI|10.1002/zaac.19432510110}} 3. ^McCleverty, J. A.; Wilkinson, G. "Dichlorotetracarbonyldirhodium (rhodium carbonyl chloride)" Inorganic Syntheses 1966, volume 8, pp. 211-14. {{DOI|10.1002/9780470132463.ch4}} 4. ^{{cite journal |last1=Nonnenmacher |first1=Michael |last2=Buck |first2=Dominik M |last3=Kunz |first3=Doris |title=Experimental and theoretical investigations on the high-electron donor character of pyrido-annelated N-heterocyclic carbenes |journal=Beilstein Journal of Organic Chemistry |date=23 August 2016 |volume=12 |pages=1884–1896 |doi=10.3762/bjoc.12.178}} 5. ^{{cite journal |last1=Huynh |first1=Han Vinh |title=Electronic Properties of N-Heterocyclic Carbenes and Their Experimental Determination |journal=Chemical Reviews |date=30 March 2018 |volume=118 |issue=19 |pages=9457–9492 |doi=10.1021/acs.chemrev.8b00067}} 5 : Organorhodium compounds|Homogeneous catalysis|Dimers (chemistry)|Carbonyl complexes|Chloro complexes |
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