SYNTHESIS AND REACITVITY OF BRIDGING THIOLATO-MANGANESE CARBONYL COMPLEXES, Et4N

Article abstract of DOI:10.1016/0022-328X(85)80224-2

The yellow-orange complexes Et4N (R= Ph, Me, t-Bu) have been prepared by several routes, including: (1) reactions of Et4N with Bu3SnSR; (2) reactions of Et4N with either Bu3SnSR, RSH, or NaSPh; and (3) reactions of Mn3(μ-X)2(CO)8 (X= Br, SPh) with NaSPh, followed by metathesis using Cl.The complex Et4Nt)3(C)6> can converted to EtnN by reaction with PhSH in the presence of either a base (pyridine) or an acid (CF3CO2H or CH3CO2H).These bridging thiolate complexes, Et4N undergo reactions with BF4 (or other electrophilic reagents) to give 4; if the same reactions are carried out in the presence of CO, Mn2(μ-SR)2(CO)8 is the product.Similarly, reactions of Et4N with BF4 in the presence of a phosphine (PMe3, dppm) produce the phosphine substituted species, cis-Mn2(μ-SR)2(CO)6(PMe3)2 and Mn2(μ-SR)2(CO)6(μ-dppm); the former is converted upon heating to the known species Mn2(μ-SR)2(μ-CO)(CO)4(PMe3)2.