DIALKYLAMINOPHOSPHORUS METAL-CARBONYLS .12. INSERTION OF PHOSPHORUS, SULFUR, AND SELENIUM INTO THE ((PR2NP)-PR-I)(2)FE-2(CO)(6) UNIT AND A NOVEL PRODUCT FROM THE REACTION OF ((PR2NP)-PR-I)(2)COFE2(CO)(6) WITH PHBCL(2)

Reactions of ((Pr2NP)-Pr-i)(2)COFe2(CO)(6) with RPCl(2) (R = (t)Bu and Ph but not (Pr2N)-Pr-i) in boiling toluene give the corresponding yel low ((Pr2NP)-Pr-i)(2)(RP)Fe-2(CO)(6) derivatives. Similar reactions of ((Pr2NP)-Pr-i)(2)COFe2(CO)(6) with PX(3)(X = Cl, Br) give the corresp onding ((Pr2NP)-Pr-i)(2)(PX)Fe-2(CO)(6) derivatives. Reaction of ((Pr2 NP)-Pr-i)(2)COFe2(CO)(6) with elemental sulfur in boiling toluene give s yellow ((Pr2NP)-Pr-i)(2)SFe2(CO)(6). Reactions of ((Pr2NP)-Pr-i)(2)C OFe2(CO)(6) with E(2)Cl(2) (E = S, Se) give ((Pr2NP)-Pr-i)(2)E(2)Fe(2) (CO)(6). Treatment of ((Pr2NP)-Pr-i)(2)COFe2(CO)(6) with boiling CCl4 results in chlorination to give light yellow ((Pr2N)-Pr-i)(2)P2Cl2Fe2( CO)(6). Reaction of ((Pr2NP)-Pr-i)(2)COFe2(CO)(6) with PhBCl(2) in boi ling toluene gives yellow [((Pr2NP)-Pr-i)(ClP)OCPh(2)]Fe-2(CO)(6). An X-ray diffraction study reveals that the structure of [((Pr2NP)-Pr-i)( ClP)OCPh(2)]Fe-2(CO)(6) is analogous to that of products previously ob tained from reactions of ((Pr2NP)-Pr-i)(2)COFe2(CO)(6) with aldehydes or ketones in which expulsion of the phosphorus-bridging carbonyl is f ollowed by addition of the phosphorus atoms across the aldehyde or ket one carbonyl, leading to a central Fe2P2OC unit.