The coordination of N,N-Diethyl-N′-p-tolyltMourea to Polynuclear Rhenium Carbonyl Complexes

Article abstract of DOI:10.1002/cber.19961290205

The reactions of Re₂(CO)₉(NCMe) and Re₃(CO)₁₀(CH₃CN)₂(μ-H) ₃ with S=C(NEt₂)N(H)(p-tolyl) have yielded the new compounds Re₂(CO)₉[S=C(NEt₂)N(H)(p-tolyl)] (1) and Re₃(CO)₁₀[μ-SC(NEt ₂)N(H)(p-tolyl)](μ-H)₃ (2) in 89% and 98% yields, respectively. Compounds 1 and 2 were characterized by single-crystal X-ray diffraction analyses. Compound 1 contains an S-coordinated S = C(NEt₂)N(H)(ptolyl) ligand terminally coordinated in an equatorial coordination site on one of the rhenium atoms. Compound 2 con-tains the first example of an S-coordinated bridging thiourea grouping. When solutions of i were heated to 97°C, it was transformed to the new compound {Re(CO)₃[μ-SC(N-ptolyl)(NEt₂)]}₂ (3) plus Re₂(CO)₁₀. Compound 3 is a centrosymmetrical dimer of the unit Re(CO)₃[SC(N-p-tolyl)(NEt₂)] in which the sulfur atom bridges the two rhenium atoms. The tolyl-substituted nitrogen atoms are coordinated to the rhenium atoms to form two Re-S-C-N rings. VCH Verlagsgesellschaft mbH 1996.