Dicarbonylchlorido(phenoxythiocarbonyl-κ2 C,S)bis(triphenylphosphane-κP)molybdenum(II)

In the title complex, [Mo(C7H5OS)Cl(C18H15P)2(CO)2], the geometry around the metal atom is a capped octahedron. The phenoxythiocarbonyl ligand coordinates the MoII atom through the C and S atoms. A one-dimensional structure is formed by π–π intermolecular interactions and a supramolecular aggregation is determined by intermolecular C—H⋯O, C—H⋯Cl, C—H⋯π(arene) hydrogen bonds and CO⋯π(arene) interactions [O⋯centroid distances = 3.485 (4) and 3.722 (3) Å].


Comment
The interest in the M-C(S)OPh moiety is due to its analogy with metallocarboxylic acid esters (M-C(O)OR) and metallocarboxylic acids themselves. Metallocarboxylic acids have been proposed to be the key intermediates in the homogeneous catalysis of the water gas shift reaction (Yoshida et al., 1978). O-Aryl thiocarbonate (Chen et al., 1978), benzoxazoline-2thione (McFarlane et al., 1998), chromene-2-thione (Zheng et al., 2006), and N,N-dimethylthiocarbamate (Zhang et al., 2004) metal complexes have been reported but few phenoxylcarbonyl metal complexes have been studied (Anderson et al., 2001). We are interested in the synthesis of dithiocarbamate, pyridine-2-thionate   (1.82 Å) single bonds (Huheey, 1983). The S1-C3-O3 group shows a geometrical environment characteristic of sp 2 hybridization of the carbon atom. In addition, the S1-C3-O3 angle of 129.0 (3)° is larger than that found in the palladium phenoxythiocarbonyl complex (125.2 (6)°) (Yih et al., 2004). To our knowledge, the title complex is the first chelating phenoxythiocarbonyl-metal complex in the literature.
In the 13 C{ 1 H} NMR spectrum of (I), two triplet resonances appear at δ 229.3 and δ 238.6 with 2 J P-C = 12.95, 11.95 Hz couplings for the two inequivalent carbonyl groups, respectively. The 31 P{ 1 H} NMR spectrum of (I) shows one resonance at δ 34.2.
It is also noted that the IR spectrum of the title complex (I) shows four stretching bands, two at 1965, 1891 cm -1 for C=O and two at 1483, 1434 cm -1 for C-OPh groups. In the FAB mass spectra, the base peak with the typical Mo isotope distribution is in agreement with the [M + ] molecular mass of (I).

Experimental
The synthesis of the title compound (I) was carried out as follows. PhOCSCl (0.135 g, 1.1 mmol) was added to a flask (100 ml) containing CH 2 Cl 2 (10 ml) and [Mo(CH 3 CN) 2 (CO) 2 (PPh 3 ) 2 ] (0.758 g, 1.0 mmol) at room temperature. The color of the solution was changed from yellow to red immediately. The solution was concentrated under vacuum and n-hexane (10 ml) was added to initiate a yellow-brown precipitation. The resulting bright-yellow solid was isolated by filtration (G4), washed with diethyl ether (2 x 10 ml) and subsequently dried under vacuum, yielding [Mo(CO) 2 (SCOPh)(PPh 3 ) 2 Cl] (0.764 g, 90%). Further purification was accomplished by recrystallization from 1/10 CH 2 Cl 2 /n-hexane. The orange crystals of (I) for X-ray structure analysis were obtained by slow diffusion of n-hexane into the CH 2 Cl 2 solution of the title compound

Refinement
H atoms were positioned geometrically and refined using a riding model, with C-H = 0.95Å and with U iso (H) = 1.2 times U eq (C). Fig. 1. The molecular structure of (I), with atom labels and the 50% probability displacement ellipsoids.