Assigment on Preparation of Metal corbonyls

Student

Miss Shahla Gul

Submitted to

Sir Saqib Kamal

DEPARTMENT OF CHEMISTRY,GOMAL UNIVERSITY, DERA ISMAIL KHAN

Preparation of metal corbonyls

The synthesis of metal carbonyls is subject of intense organometallic research. Since the work of Mond and then Hieber, a lotof procedures have been developed for the preparation of mononuclear metal carbonyls as well as homo-and hetero-metallic carbonyl clusters.[26]

Direct reaction of metal with carbon monoxide

Nickel tetracarbonyl and iron pentacarbonyl can be prepared according to the following equations by reaction of finely divided metal with carbon monoxide:[27] Ni + 4 CO Ni(CO)4 (1 bar, 55 C) Fe + 5 CO Fe(CO)5 (100 bar, 175 C) Nickel carbonyl is formed with carbon monoxide already at 80 C and atmospheric pressure, finely divided iron reacts at temperatures between 150 and 200 C and a carbon monoxide pressure of 50 to 200 bar.[28] Other metal carbonyls are prepared by less direct methods.

Reduction of metal salts and oxides

Some metal carbonyls are prepared by the reduction of metal halides in the presence of high pressures of carbon monoxide under pressure. A variety of reducing agents are employed, including copper, aluminum, hydrogen, as well as metal alkyls such as triethylaluminum. Illustrative is the formation of chromium hexacarbonyl from anhydrouschromium(III) chloride in benzene with aluminum as a reducing agent, and aluminum chloride as the catalyst:[27] CrCl3 + Al + 6 CO Cr(CO)6 + AlCl3 The use of metal alkyls, e.g. triethylaluminium and diethylzinc as the reducing agent leads to the oxidative coupling of the alkyl radical to the dimer: WCl6 + 6 CO + 2 Al(C2H5)3 W(CO)6 + 2 AlCl3 + 3 C4H10 Tungsten, molybdenum, manganese, and rhodium salts may be reduced with lithium aluminum hydride. Vanadium hexacarbonyl is prepared with sodium as a reducing agent inchelating solvents such as diglyme.[7] VCl3 + 4 Na + 6 CO 2 diglyme Na(diglyme)2[V(CO)6] + 3NaCl [V(CO)6] + H+ H[V(CO)6] 1/2 H2 + V(CO)6 In aqueous phase nickel or cobalt salts can be reduced, for example, by sodium dithionite. In the presence of

carbon monoxide, cobalt salts are quantitatively converted to the tetracarbonylcobalt(-1) anion:[7] Co2+ + 1.5 S2O42 + 6 OH + 4 CO Co(CO)4 + 3 SO32 + 3H2O Some metal carbonyls are prepared using CO as the reducing agent. In this way, Hieber and Fuchs first prepared dirhenium decacarbonyl from the oxide:[29] Re2O7 + 17 CO Re2(CO)10 + 7 CO2 If metal oxides are used carbon dioxide is formed as a reaction product. In the reduction of metal chlorides with carbon monoxide phosgene is formed, as in the preparation ofosmium carbonyl chloride from the chloride salts.[26] Carbon monoxide is also suitable for the reduction of sulfides, where carbonyl sulfide is the byproduct.

Photolysis and thermolysis

Photolysis or thermolysis of mononuclear carbonyls generates bi- and multimetallic carbonyls such as diiron [30][31] nonacarbonyl (Fe2(CO)9). On further heating, the products decompose eventually into

the metal and carbon monoxide. 2 Fe(CO)5 Fe2(CO)9 + CO The thermal decomposition of triosmium dodecacarbonyl (Os3(CO)12) provides highernuclear osmium carbonyl clusters such as Os4(CO)13, Os6(CO)18 up to Os8(CO)23.[7] Mixed ligand carbonyls of ruthenium, osmium, rhodium, and iridium are often generated by abstraction of CO from solvents such as dimethylformamide (DMF)and 2methothol Typical is the synthesis of IrCl(CO)(PPh3)2 from the reaction of iridium(III)chloride and triphenylphosphie in boiling DMF solution.

Salt metathesis
Salt metathesis reaction of for example KCo(CO)4 with [Ru(CO)3Cl2]2 leads selectively to mixed-metal carbonyls such as RuCo2(CO)11.[32] KCo(CO)4 + [Ru(CO)3Cl2]2 2 RuCo2(CO)11 + 4 KCl

Metal carbonyl cations and carbonylates

The synthesis of ionic carbonyl complexes is possible by oxidation or reduction of the neutral complexes. Anionic metal carbonylates can be obtained for example by reduction of dinuclear complexes with sodium. A familiar example is the sodium salt of iron tetracarbonylate (Na2Fe(CO)4,Collman's reagent), which is used in organic synthesis.[33] The cationic hexacarbonyl salts of manganese, technetium and rhenium can be prepared from the carbonyl halides under carbon monoxide pressure by reaction with a Lewis acid. Mn(CO)5Cl + AlCl3 + CO Mn(CO)6+AlCl4 The use of strong acids succeeded in preparing gold carbonyl cations such as [Au(CO)2]+, which is used as a catalyst for the carbonylation of olefins.[34] The cationic platinum carbonyl complex [Pt(CO)4]+ can be prepared by working in so-called super acids such as antimony pentafluoride