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Organic chemistry of Dinuclear Metal Centres. Part 8. Organo-Iron-Ruthenium Chemistry. X-Ray Structure of trans-

DOI: 10.1039/DT9850001935

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1935 - 1944 (1985)

Update date:2022-08-16

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Authors:

Gracey, BenjaminGracey, Benjamin

Knox, Selby A. R.Knox, Selby A. R.

Macpherson, Kirsty A.Macpherson, Kirsty A.

Orpen, Guy A.Orpen, Guy A.

Stobart, StephenStobart, Stephen

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Article abstract of DOI:10.1039/DT9850001935

The iron-ruthenium complex is obtained in 60 percent yield from the reaction of Na with .In the solid state a trans- structure has been established by X-ray diffraction.Crystals are monoclinic, space group P21/c (no. 14), with Z=2 in a unit cell for which a=7.064(2), b=12.518(3), c=8.011(2) Angstroem, and β=106.23(2) deg.The structure was solved by heavy-atom methods and refined to R 0.0275 (R' 0.0313) for 1532 independent intensities.The molecule is disordered about a centre of inversion at the mid-point of the metal-metal bond, each metal site being occupied by half an iron and half a ruthenium atom, with an iron-ruthenium bond length of 2.626(1) Angstroem.In solution the cis- isomer is dominant, and shown by 13C n.m.r. to be undergoing cis <*> trans isomerisation with bridge <*> terminal carbonyl exchange at room temperature, but to be static at -80 deg C.The complex is an excellent precursor of organo-iron-ruthenium chemistry.Treatment with alkynes R1C2R2 (R1 = R2 = H, Me, or Ph, R2 = H) under u.v. irradiation gives complexes 1CR2>(η-C5H5)2> in 20-65 percent yield as a result of alkyne-CO linkage.This link in the complexes derived from ethyne, propyne, and but-2-yne is broken upon protonation, generating μ-vinyl cations 1=CHR2)(η-C5H5)2>+ (R1 = R2 H or Me; R1 = H, R2 = Me).These are attacked by hydride at the β carbon of the μ-vinyl to give μ-alkylidene complexes 1R2)(μ-C5H5)2> (R1 = H, R2 = Me, Et; R1 = Me, R2 = Et).Reaction of (η-C5H5)2> with Ph3P=CHR or CH(CO2Et)N2 in boiling toluene also gives μ-alkylidene complexes (R = H, Me, or CO2Et) in good yield, through ready displacement of diphenylacetylene.The μ-CH2 complex is best obtained (75 percent) by trating with LiBHEt3 then water, and in a related manner sequential addition of methyl-lithium, HBF4*OEt2, and NaBH4 affords .Under u.v. irradiation alkynes react with μ-alkylidene complexes 1)(η-C5H5)2> to give products of alkyne-alkylidene linking 3CR2CR1)(η-C5H5)2> (R1 = H or Me, R2 = R3 = H, Me, Ph, or CO2Me; R1 = H or Me, R2 = Me or Ph, R3 = H).These exist as non-interconverting isomers in which the new C3 ligand is either bound ? to iron and and ?, η2 to ruthenium or vice versa.The scope of organo-iron-ruthenium chemistry closely resembles that of the di-iron system but it is apparent that in reactivity terms there is an order: FeRu > Fe2 > Ru2.

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