Reactions of [Mn2(μ-pyS)2(CO)6] with bidentate phosphines: X-ray structure of [Mn(η2-pyS) (η2-dppp)(CO)2] [dppp = Ph2P(CH2)3PPh2, pySH = pyridine-2-thiol

Abstract

The dimeric complex [Mn2(μ-pyS)2(CO)6] (1) reacted with 2 molar equivalents of Ph2P(CH2)3PPh2 (dppp) and Ph2P(CH2)2PPh2 (dppe) to give the respective monomeric chelate complexes [Mn(η2-pyS)(η2-dppp)(CO)2] (2) and [Mn(η2-pyS)(η2-dppe)(CO)2] (3). In contrast, with 2 molar equivalents of Ph2P(CH2)5PPh2 (dpppe), 1 gave the highly insoluble polymeric complex [Mn(η2-pyS)(μ-dpppe)(CO)2]n (4). An X-ray structure determination shows that 2 crystallizes in the monoclinic space group P21/n with a = 10.721(2) A, b = 19.712(5) A, c = 14.846(4) A, β = 109.06(2)°, V = 2965.5(14) A3, and Z = 4. The complex has a distorted octahedral geometry with the dppp ligand, one CO group and the N atom of the chelating pyS ligand occupying equatorial sites, and one CO group and the S atom of the pyS ligand lying in the axial positions.