(ARENE)TRICARBONYLMANGANESE(I) COMPLEXES - A PREPARATIVE STUDY - CRYSTAL-STRUCTURE OF [(ETA-6-C6H5CH2COCH2PH)MN(CO)3]BF4

The scope of [(eta6-arene)Mn(CO)3]+ synthesis is investigated. Methods of preparation involve abstraction of bromide from [Mn(CO)5Br] by AlCl3 or Ag(I) or, alternatively, oxidation of [Mn2(CO)10] by strong acid. Arenes which bear the following substituents can be coordinated: alkyl, aryl, alkoxy, chloro, hydroxy, fused heterocycle aromatic rings, and nonconjugated carbonyl. The degree of electron donation to the ring is the principal factor in determining the likelihood of coordination. Highly electron-deficient aromatics such as nitro, cyano, and those conjugated to carbonyls will not metalate. The use of aluminum chloride leads to the rearrangements of some alkylbenzenes and substitution reactions of some aryl halides. In the case of o-dichlorobenzene, this substitution yields the unusual complex [eta6-2-ClC6H4Mn(CO)5Mn(CO)3]+. Other new complexes reported include those of dibenzothiophene, 1,3-diphenylacetone, deoxybenzion, and phenol. A crystal structure of [(eta6-C6H5CH2COCH2Ph)Mn(CO)3]BF4 is reported: space group P2(1)/c, a = 12.5429(12) angstrom, b = 12.465(2) angstrom, c = 12.109(2) angstrom, beta = 106.128(10)-degrees, V = 1818.8(5) angstrom3, Z = 4, D(calc) = 1.592 mg m-3, R = 0.0570, and omegaR2 = 0.1609 on 2331 reflections with F2 > 2.0sigma(F2).