Inorganica Chimica Acta p. 1 - 11 (1998)
Update date:2022-08-04
Topics:
Hartl, Frantiek
The five-coordinate anion [Mn(CO)3(DBCat)]- has been found to undergo nucleophilic CO substitution reactions with L = PR3, P(OR)3 producing the dicarbonyl derivatives [Mn(CO)2(L)(DBCat)]-. The reaction yield is higher for better nucleophiles such as L = PEt3 and P(OEt)3; the latter species reacts quantitatively even when added in an equivalent amount. Contrary to this, bulky phosphines with the cone angle θ≥ 145°, namely L = PPh3, PCy3, do not show this reaction but interact reversibly with [Mn(CO)3(DBCat)]- at low temperatures to give the six-coordinate adducts [Mn(CO)3(DBCat) · L]-. For L = pyridine the corresponding adduct is already formed at room temperature. Similarly, [Mn(CO)2(P(OEt)3)(DBCat)]- takes up reversibly P(OEt)3. The spectroscopic and redox properties of the adducts closely correspond with those of the invariably six-coordinate anions [Re(CO)4-n(L)n(DBCat)]- (n = 1, 2). The uptake of a Lewis base by [Mn(CO)3(DBCat)]- is facilitated by an electrophilic attack at the oxygen lone pairs of the σ,π-donor DBCat ligand. Examples are the anions [Mn(CO)3(L)(DBCat·BF3)]- (L = THF, PPh3) and [Mn(CO)3(PPh3) (DBCat·CS2)]- which are inherently stable at ambient temperature. This reactivity is closely related to the DBCat-localized le oxidation of [Mn(CO)3(DBCat)]- producing six-coordinate radical s [Mn(CO)3(L)(DBSQ)]. The electrophilic attack of CS2 at the DBCat ligand has also been documented by the conversion of [Mn(CO)3(DBCat)]- in the absence of PPh3 to the trithiocarbonate complex [Mn(CO)4(S2CS)]- and uncoordinated 4,6-di-tert-butyl-1,3-benzdioxol-2-thione. 1998 Elsevier Science S.A.
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