MO, W) - LIGAND SUBSTITUTION-REACTIONS AND X-RAY CRYSTAL-STRUCTURE OF [ET4N]2[W2(CO)8(SPH)2] SYNTHESIS AND CHARACTERIZATION OF [ET4N][M(CO)5SR] AND [ET4N]2[M2(CO)8(SR)2] COMPLEXES (M = CR

A series of complexes, [Et4N][M(CO)5SR] (M = Cr, Mo, W; R = H, Ph), have been synthesized and characterized by 1H and 13C NMR and IR spectroscopies. Gentle heating causes these complexes to lose a carbonyl ligand, yielding the doubly bridged sulfur dimers M2(CO)8(-SR)22-. The X-ray crystal structure of [Et4N]2[W2(CO)8(SPh)2] has been determined. The complex crystallizes in the triclinic space group P1 with unit cell parameters a = 9.8664 (17) , b = 9.8566 (22) , c = 11.8270 (26) , = 65.790 (16), = 81.710 (16), = 82.000 (16), V = 1034.0 (4) 3, and Z = 1. Both mono- and dinuclear metal complexes readily react with phosphorus donor ligands to afford the carbon monoxide substituted complexes cis-M(CO)4(P)(SR)- (P = PMe3, P(OMe)3, PPh3). In addition, the dimers react with 1 atm of carbon monoxide to re-form the mononuclear species M(CO)5SR- in quantitative yields. Unsuccessful attempts to insert CO2, COS, or CS2 into the M-SR bond in the M(CO)5SR- derivatives are noted. 1988, American Chemical Society. All rights reserved.

SYNTHESIS AND CHARACTERIZATION OF [ET4N][M(CO)5SR] AND [ET4N]2[M2(CO)8(SR)2] COMPLEXES (M = CR, MO, W) - LIGAND SUBSTITUTION-REACTIONS AND X-RAY CRYSTAL-STRUCTURE OF [ET4N]2[W2(CO)8(SPH)2] Academic Article