Dialkylaminophosphorus metal carbonyls. 12. Insertion of phosphorus, sulfur, and selenium into the (iPr2NP)2Fe2(CO)6 unit and a novel product from the reaction of (iPr2NP)2COFe2(CO)6 with PhBCl2

Article abstract of DOI:10.1016/0022-328X(94)00007-Y

Reactions of (ⁱPr2NP)2COFe2(CO)6 with RPCl2 (R = ^tBu and Ph but not ⁱPr2N) in boiling toluene give the corresponding yellow (ⁱPr2NP)2(RP)Fe2(CO)6 derivatives.Similar reactions of (ⁱPr2NP)2COFe2(CO)6 with PX3 (X= Cl, Br) give the corresponding (ⁱPr2NP)2(PX)Fe2(CO)6 derivatives.Reaction of (ⁱPr2NP)2COFe2(CO)6 with elemental sulfur in boiling toluene gives yellow (ⁱPr2NP)2SFe2(CO)6.Reactions of (ⁱPr2NP)2COFe2(CO)6 with E2Cl2 (E= S, Se) give (ⁱPr2NP)2E2Fe2(CO)6.Treatment of (ⁱPr2NP)2COFe2(CO)6 with boiling CCl4 results in chlorination to give light yellow (ⁱPr2N)2P2Cl2Fe2(CO)6.Reaction of (ⁱPr2NP)2COFe2(CO)6 with PhBCl2 in boiling toluene gives yellow <(ⁱPr2NP)(ClP)OCPh2>Fe2(CO)6.An X-ray diffraction study reveals that the structure of <(ⁱPr2NP)(ClP)OCPh2>Fe2(CO)6 is analogous to that of products previously obtained from reactions of (ⁱPr2NP)2COFe2(CO)6 with aldehydes or ketones in which expulsion of the phosphorus-bridging carbonyl is followed by addition of the phosphorus atoms across the aldehyde or ketone carbonyl, leading to central Fe2P2OC unit. Keywords: Iron; Carbonyl; Phosphorus; Sulfur; Selenium; Boron