Dirhenium decacarbonyl

Structural formula
General
Surname	Dirhenium decacarbonyl
Molecular formula	Re 2 (CO) 10
Brief description	pale yellow solid
External identifiers / databases
EC number	238-202-8
ECHA InfoCard	100.034.714
PubChem	498777
ChemSpider	436546
Wikidata	Q418221
properties
Molar mass	652.52 g mol −1
Physical state	firmly
density	2.87 g cm −3 (20 ° C)
Melting point	170 ° C
solubility	almost insoluble in water
safety instructions
GHS labeling of hazardous substances Caution
H and P phrases	H: 332
	P: no P-phrases
	As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Dirhenium decacarbonyl (often also referred to as rhenium decacarbonyl ) was the first known stable metal carbonyl of the element rhenium and was synthesized in 1941 by Hieber , who is considered a pioneer in metal carbonyl chemistry.

presentation

The solid is produced from rhenium (VII) oxide directly by reduction with carbon monoxide .

{\ displaystyle \ mathrm {Re_ {2} O_ {7} +17 \ CO \ longrightarrow \ Re_ {2} (CO) _ {10} +7 \ CO_ {2}}}

It can also be obtained from potassium rhenate .

{\ displaystyle \ mathrm {KReO_ {4} +17 \ CO \ longrightarrow \ Re_ {2} (CO) _ {10} +6 \ CO_ {2} + K_ {2} CO_ {3}}}

properties

Re ₂ (CO) ₁₀ is a metal carbonyl with a metal-to-metal bond and is therefore to be regarded as a metal cluster according to Cotton's definition . The equatorial carbonyl ligands of the rhenium fragment Re (CO) ₅ present in oxidation state 0 have a staggered arrangement with respect to one another in the molecule. The metal-to-metal bond length is 304 pm and was determined from the data of a single crystal X-ray structure analysis.

Re ₂ (CO) ₁₀ fulfills the 18-electron rule : (Rhenium has 7 outer electrons (14), each carbonyl ligand controls 2 electrons in (20), the metal-metal bond has 2 electrons: 14 + 20 + 2 = 36).

It is in the form of air-stable, colorless leaves (made from petroleum ether). At higher temperatures, decomposition occurs with metal deposition. It is insoluble in water, moderately soluble in aliphatic hydrocarbons and readily soluble in tetrahydrofuran and methylene chloride .

Reactions

A classic reaction to anionic carbonyl is the base reaction to Hieber . During this reaction, the base OH ^- attacks the carbonyl C atom, the primary addition product decomposes and the carbonyl metalate is formed. This is how HRe (CO) ₅ is created, for example .

If dirhenium decarcarbonly or its homologous compounds Mn ₂ (CO) ₁₀ or Tc ₂ (CO) _{10 are} reacted with halogens, the carbonyl halides are obtained: M ₂ (CO) ₁₀ + Hal ₂ → 2 HalM (CO) ₅ . In this way, BrMn (CO) ₅ , ClMn (CO) ₅ , ClRe (CO) ₅ and BrRe (CO) ₅ etc. are available.

The combination of the two processes mentioned serves to synthesize mixed metal carbonyls: BrMn (CO) ₅ + ^- Re (CO) ₅ → MnRe (CO) ₁₀

Further reactions are based on ligand exchange reactions and / or thermal or photochemical treatment of the carbonyls.

use

The substance is used as a starting molecule for other rhenium compounds, especially for clusters, since the CO ligands can easily be exchanged for other ligands.

Individual evidence

↑ David R. Lide (Ed.): CRC Handbook of Chemistry and Physics . 90th edition. (Internet version: 2010), CRC Press / Taylor and Francis, Boca Raton, FL, Physical Constants of Inorganic Compounds, pp. 4-84.
↑ ^a ^b ^c ^d data sheet dirhenium decacarbonyl from AlfaAesar, accessed on February 9, 2010 ( PDF )(JavaScript required) .
↑ ^a ^b Data sheet Dirhenium decacarbonyl from Sigma-Aldrich , accessed on March 28, 2011 ( PDF ).
^ W. Hieber, H. Fuchs: About metal carbonyls. XXXVIII. About rhenium pentacarbonyl. In: Z. Anorg. General Chem. , 1941 , 248 , 256-268; doi : 10.1002 / zaac.19412480304
↑ ^a ^b Georg Brauer (Ed.) U. a .: Handbook of Preparative Inorganic Chemistry. 3rd, revised edition. Volume III, Ferdinand Enke, Stuttgart 1981, ISBN 3-432-87823-0 , p. 1826.
↑ MR Churchill, KN Amoh, HJ Wasserman: Redetermination of the crystal structure of dimanganese decacarbonyl and determination of the crystal structure of dirhenium decacarbonyl. In: Inorg. Chem. 1981 , 20 , 1609-1611; doi : 10.1021 / ic50219a056
↑ BH Byers, TL Brown: The characteristics of M (CO) 5 and related metal carbonyl radicals; abstraction and dissociative and oxidative addition processes. In: J. Am. Chem. Soc. 1977 , 99 , 2527-2532; doi : 10.1021 / ja00450a020

literature

Christoph Elschenbroich , A. Salzer: Organometallchemie . Teubner Taschenbücher Chemie, 1990. ISBN 3-519-23501-3

[CRC90_5_6-1] David R. Lide (Ed.): CRC Handbook of Chemistry and Physics . 90th edition. (Internet version: 2010), CRC Press / Taylor and Francis, Boca Raton, FL, Physical Constants of Inorganic Compounds, pp. 4-84.

[alfa-2] ta sheet dirhenium decacarbonyl from AlfaAesar, accessed on February 9, 2010 ( PDF )(JavaScript required) .

[Sigma-3] Data sheet Dirhenium decacarbonyl from Sigma-Aldrich , accessed on March 28, 2011 ( PDF ).

[4] W. Hieber, H. Fuchs: About metal carbonyls. XXXVIII. About rhenium pentacarbonyl. In: Z. Anorg. General Chem. , 1941 , 248 , 256-268; doi : 10.1002 / zaac.19412480304

[brauer-5] Georg Brauer (Ed.) U. a .: Handbook of Preparative Inorganic Chemistry. 3rd, revised edition. Volume III, Ferdinand Enke, Stuttgart 1981, ISBN 3-432-87823-0 , p. 1826.

[6] MR Churchill, KN Amoh, HJ Wasserman: Redetermination of the crystal structure of dimanganese decacarbonyl and determination of the crystal structure of dirhenium decacarbonyl. In: Inorg. Chem. 1981 , 20 , 1609-1611; doi : 10.1021 / ic50219a056

[7] BH Byers, TL Brown: The characteristics of M (CO) 5 and related metal carbonyl radicals; abstraction and dissociative and oxidative addition processes. In: J. Am. Chem. Soc. 1977 , 99 , 2527-2532; doi : 10.1021 / ja00450a020