Reactions of [Mn2(μ-pyS)2CO6] with bidentate phosphines:: X-ray structure of [Mn(η2-pyS) (η2-dppp)(Co)2] [dppp = Ph2P(CH2)3PPh2, pySH = pyridine-2-thiol]

The dimeric complex [Mn-2(mu -pyS)(2)(CO)(6)] (1) reacted with 2 molar equivalents of Ph2P(CH2)(3)PPh2 (dppp) and Ph2P(CH2)(2)PPh2 (dppe) to give the respective monomeric chelate complexes [Mn(eta (2)-pyS) (eta (2)-dppp)(CO)(2)] (2) and [Mn(eta (2)-pyS)(eta (2)-dppe)(CO)(2)] (3). In contrast, with 2 molar equivalents of Ph2P(CH2)(5)PPh2 (dpppe), 1 gave the highly insoluble polymeric complex [Mn(eta (2)-pyS)(mu -dpppe)(CO)(2)]n (4). An X-ray structure determination shows that 2 crystallizes in the monoclinic space group P2(1)/n with a = 10.721(2) Angstrom, b = 19.712(5) Angstrom, c = 14.845(4) Angstrom, beta = 109.06(2)degrees, V = 2965.5(14) Angstrom (3), 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 acid the S atom of the pyS ligand lying in the axial positions.