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Synthesis and reactions of the [(.mu.-Ph2P)Fe2(CO)6]- anion

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Abstract (summary)

The action of 2 molar equiv of LiBE^H on 0i-CH3C=O)0i-Ph2P)Fe2(CO)6 gives a reactive species which IR spectroscopic evidence suggests to be Li[(/i-Ph2P)Fe2(CO)6]. This species reacts with acid halides, RC(0)C1, Me2NC(S)Cl, Me2P(S)Cl, and chlorophosphines; neutral products of type 0t-E)0i-Ph2P)Fe2(CO)6 (E = RC=0, Me2NC=S, Me2P=S, R^) were obtained in good yield. Reaction with CS2 and RNCS gave anionic products, 0t-SC==S)0t-Ph2P)Fe2(CO)6 and Ot-RÑO=S)Ot-Ph2P)Fe2(CO)6. The [Oi-Ph2P)Fe2(CO)8]~ reagent is much more reactive than the known [^-CO)(p-Ph2P)Fe2(CO)6]~. The structure of (µCH3)2P==S)0t-PhS)Fe2(CO)6 (18b) has been determined by X-ray techniques. Compound 18b crystallizes in the orthorhombic space group P212121 with o = 12.494 (2) k,b- 17.075 (2) Á, c = 8.7909 (9) k,V1944.7 (7) Á3, and Z = 4. The two Fe(CO)3 groups in the complex are bridged by the benzenethiolate and the dimethylphosphino sulfide groups, the latter of which is S-bound to one metal and P-bound to the other. Within the SPMe2 ligand the P—S distance of 2.030 (2) A lies intermediate between that of a single (2.18 A) and a double (1.95 A) bond.

Publication Information

Seyferth, D., Brewer, K., Wood, T., Cowie, M., & Hilts, R. (1992). Synthesis and reactions of the [(.mu.-Ph2P)Fe2(CO)6]- anion. Organometallics, 11(7), 2570–2579.


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