Coordination and organometallic complexes of iron containing ö-phenylenebis(dimethylphosphine) (pdmp). Crystal and molecular structure of [Fe(η2-C₂H₄)(pdmp)₂]

Routes to hydrido- and organo-iron complexes of the bidentate ligand o-phenylenebis(dimethylphosphine), o-C6H4(PMe2)2 (pdmp), have been developed, starting from trans-[FeCl₂(pdmp)2]. Reduction of trans-[FeC\2(pdmp)2] with LiAlH4 gives the dihydride, cw-[FeH2(pdmp)2], there being no evidence for an intermediate monohydride [FeHCl(pdmp)2]. Treatment of /ra/w-[FeCl₂(pdmp)₂] with an excess of methyllithium gives [FeMe2(pdmp)2], isolated as a cis//ra;;s-mixture, the methyl groups of which are cleaved by an excess of HX to give [FeX2(pdmp)₂] (X = Cl, Br), predominantly in the form of the c/s-isomers. Other new complexes include [FeCI(Me)(pdmp)2] (m//ra;u-mixture) and [Fe(L)(pdmp)2] [L = CO, T|2-C2H4, n2-C8H8, nM,4-C8H6(SiMe3)2, r]2-C4H6, r|2-PhC2Ph and r|2-MeC₂Me]. Treatment of/ra/j.c-[FeCl2(pdmp)2] with sodium-naphthalene generates the hydrido(naphthyl)iron(n) complex [FeH(r(1-CIOH7)(pdmp)2] as a cis/trans-mixlute in tautomeric equilibrium with a zerovalent iron naphthalene complex [Fe(r|2-C,0H8)(pdmp)2]. Single crystal X-ray analysis shows that [Fe(n2-C2H4)(pdmp)2] has a distorted octahedral structure in which the ethylene is twisted by ca. 15° relative to the FeP4 skeleton, probably because of steric effects. In solution the coordinated ethylene rotates about the coordination axis with a free energy of activation ΔC^t at 324 K of 67 kJ mol^-1, as estimated from variable temperature 'H and 31P NMR spectra. In the cyclooctatetraene complexes [Fe(r|2-C8Hg)(pdmp)2] and [Fe{(nM,4C8H6)(SiMe3)2}(pdmp)2] there is also a lower energy process in which the Fe(pdmp)2 unit migrates between the double bonds of the eight-membered ring. The strong electron-donating ability of the Fe(pdmp)2 fragment is indicated by the low value of v(CO) in [Fe(CO)(pdmp)2], the highly shielded 'H and I3C nuclei of coordinated ethylene in [Fe(n2-C2H4)(pdmp)2], the Fe-C and C=C bond lengths in the Fe-C2H4 unit [2.052(8) and 1.418(10) A, respectively], and the facile reversible protonation of the coordinated ethylene by methanol or ethanol. Treatment of [Fe(n2-C2H4)(pdmp)2] with HBF4-OEt2 gives initially a complex ris-[Fe(BF4)(Et)(pdmp)2], in which the ethyl group may be agostic, and finally râ-[Fe(BF4)2(pdmp)2]. The coordinated BF4 groups of the latter compound are displaced by acetonitrile to give c/5-[Fe(NCMe)2(pdmp)2](BF4)2. The BPh4 salts of the cations [FeBr(NCMe)(pdmp)2]'1' and [Fe(NCMe)2(pdmp)2]2+ have also been isolated as mixtures of cis/trans-isomers from râ-[FeX2(pdmp)2] (X = Cl, Br) and acetonitrile.