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Reaction of the Metallacycle n)S>(1+) with Nucleophiles. X-Ray Crystal Structures of the Comlexes n)S>SO3CF3 and SC(FeLn)S>n = Fe(cp)(CO)2, cp = η-C5H5>

DOI: 10.1039/DT9880001067

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1067 - 1074 (1988)

Update date:2022-08-11

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Authors:

Busetto, LuigiBusetto, Luigi

Zanotti, ValerioZanotti, Valerio

Albano, Vincenzo G.Albano, Vincenzo G.

Braga, DarioBraga, Dario

Monari, MagdaMonari, Magda

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Article abstract of DOI:10.1039/DT9880001067

Reactions of the metallacyclic cation <(OC)(cp)FeC(SMe)SC(FeLn)S>(1+)n = Fe(cp)(CO)2, cp = η-C5H5> with nucleophilic agents have been investigated.The results indicate that the carbene carbon atom bonded to the endocyclic iron is the site of addition of all the nucleophiles examined.Primary amines NH2R (R = Me, C6H11, or n-Bu) form neutral isocyanide derivatives <(CO)(RNC)(cp)FeSC(S)FeLn> with opening of the FeC2S2 ring, whereas secondary amines such as NHR2 (R = Me or Et) or HN(CH2)nCH2 (n = 3 or 4) produce stable cationic cyclic aminothiocarbenes.The structure of one of these, <(OC)(cp)FeC(NC5H10)SC(FeLn)S>SO3CF3, has been determined by X-ray diffraction a = 11.570(2), b = 12.242(2), c = 10.552(2) Angstroem, α = 104.60(2), β = 87.51(1), γ = 117.24(2) deg, Z = 2, and space group P1>.The cation contains the five-membered planar ring FeSCSC with the Fe(cp)(CO)2 and NC5H10 groups bonded to the carbon atoms.The C(carbene)-N interaction exhibits strong double-bond character <1.32(1) Angstroem>, typical for an iminium cation.Methanethiol, Li(BHEt3), and KCN yield neutral <(OC)(cp)FeCX(SMe)SC(FeLn)S> (X = SMe, H, or CN).In the hydride addition an isomeric mixture has been ascertained by i.r. and n.m.r. spectra, whereas the cyanide ion adds steroselectively at the prochiral carbene centre to form only one diastereoisomer whose steric nature has been determined by X-ray diffraction a = 6.894(2), b = 10.057(1), c = 14.520(2) Angstroem, α = 96.00(2), β = 96.17(1), γ = 106.31(1) deg, Z = 2, and space group P1>.In this derivative the FeSCSC ring undergoes substantial changes because the iron-bonded carbon atom becomes four-co-ordinate with loss of its carbenic character and significant out-of-plane displacement.A comparative analysis of the relevant geometric features of all the members of this family is reported.Propane-1,3-dithiol produces the neutral spirocyclic <(CO)(cp)FeCSC(FeLn)S> which shows equivalence of the two diastereotopic SCH2 carbons in the high-temperature 13C n.m.r. spectrum and splitting of ν(CO) in the i.r. spectrum.These spectroscopic features are discussed and interpreted.

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