[Mn(CO)3(R2PCH2)3CCH3]ClO4 (1a) (R = C6H5) reacts with NaBH4 on UV irradiation to yield HMn(CO)2(R2PCH2)3CCH3 (2a). [Mn(CO)3(R2PCH2)3CCH3]BR4 (1b) gives only decomposition products. Boiling of 1a or b and NaOH in acetone/water does nots give 2a but the new hydride HMn(CO)3(R2PCH2)2C(CH3)CH2PR2 (3a). This compound cannot be prepared on ultraviolet irradiation of a solution of 1a or b and NaBH4 in methyl alcohol or acetone. The analogous deutendes DMn(CO)2(R2)PCH2)3CCH3 (2b) and DMn(CO)3(R2PCH2)2C(CH3)CH2PR2 (3b) were also prepared. The new compounds were characterized by their IR, Raman, 1H NMR and 31P NMR spectra.
Decacarbonyldimanganese reacts with the tritertiary phosphine 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos) to give the ionic complex [Mn(CO)3triphos][Mn(CO)5]. Treatment of [Mn(CO)3triphos][Mn(CO)5] with Na[B(C6H5)4], HClO4 and NH4PF6 yields the manganese(I) salts [Mn(CO)3triphos]Y (Y = B(C6H5)4, ClO4, PF6). The IR (2100-300 cm-1) and FIR spectra (350-200 cm-1) of all compounds are reported. Based on Raman polarization data the assignment of the v(CO) (A1 + E), δ(MnCO) (A1 + 2 E), v(MnC) (A1 + E) and v(MnP) (A1) modes was possible for the coordination polyhedra cis-Mn(CO)3P3(point group C3v). The v(MnP) (E) mode was unobserved due to its very low frequency.