90245-08-2Relevant academic research and scientific papers
Synthetic, structural, and chemical study of some η5-phosphacyclohexadienyl complexes with iron and manganese
Deschamps, Eliane,Mathey, Fran?ois,Knobler, Carolyn,Jeannin, Yves
, p. 1144 - 1150 (2008/10/08)
The reaction of Mn2(CO)10 with 4,5-dimethyl-1,2-diphenyl-1,6-dihydrophosphorin P-sulfide (5) (HL=S) gives HL→Mn2(CO)9 (8) through reduction-complexation of the P=S bond and (η5-L=S)Mn(CO)3 (9) through metalation and η5-C5 complexation of the dihydrophosphorin ring. Upon heating the HL→Mn2(CO)9 complex undergoes an orthometalation of the P-phenyl substituent with loss of HMn(CO)5. The reaction of Mn2(CO)10 with the corresponding oxide (HL=O) (12) gives only the η5-C5 complex (η5-L=O)Mn(CO)3 (13), in high yield, since the P=O bond cannot be reduced. Similarly, HL=O reacts with [CpFe(CO)2]2 to give (η5-L=O)FeCp (14). The reaction of this sandwich complex with n-butyllithium leads to a replacement of the P-Ph by a P-n-Bu substituent. The acylation by CH3COCl + AlCl3 takes place selectively on the Cp ring. The X-ray crystal structure of 14 shows that the Fe-C distances range from 2.05 to 2.13 A? for the heterocycle and from 2.06 to 2.11 A? for the cyclopentadienyl ring. The two planes are nearly parallel (dihedral angle = ～2.2°). The phosphorus atom is out of the C5 plane by 0.733 (3) A? on the opposite side of iron, and the folding of the heterocyclic ligand around the C-Cα′ axis is 38.5°. There is no direct interaction between the iron atom and the endo phosphoryl oxygen.
