ORGANIC-REACTIONS UPON DIMETALLATED OLEFINS - REACTIONS OF THE OLEFINIC GROUP IN THE DIRHENIUM COMPLEX (OC)(4)RE[E-HC=C(CO(2)ME)CS2]RE(CO)(4) WITH AMINES

The reaction of (OC)(4)Re[mu-E-HC=C(CO(2)Me)CS2]Re(CO)(4), 1 with EtNH(2) yielded two new complexes: Re(Co)(4)[C(H)=C(CO(2)Me)C(NHEt)=S], 2, (52%) and Re(CO)(3)(NH(2)Et)[C(H)=C(CO(2)Me)C(NHEt)=S], 3a (24%) by competitive attack of the EtNH(2) at the dithiocarboxylate grouping and at the hydrogen substituted olefinic carbon atom in 1. In both cases there is a loss of one of the rhenium groupings. The reaction of the sulfurized and oxygenated derivatives of 1, (OC)(4)Re[EC(H)C(CO(2)Me)CS2]Re(CO)(4), 4a (E=S), 4b (E=O) with EtNH(2) yielded Re(CO)(4)[C(H)=C(CO(2)Me)C(NHEt)=S], 5a, the parent carbonyl of 3a, by exclusive attack of the amine at the hydrogen substituted olefinic carbon atom. The reaction of (OC)(4)Re[mu-SC(s)C(CO(2)Me)C(H)S]Re(CO)(4), 6a (an isomer of 4a) with EtNH(2) produced a similar result. The reaction of 4a with Et(2)NH yielded Re(CO)(4) [mu-S2C=C(CO(2)Me)C=NEt(2)], 5b an N-ethyl substituted derivative of 5a. These results indicate that the addition of certain heteroatoms can have a directing effect upon the reactivity of these compounds with amines. Compounds 2 and 5a were characterized by single crystal x-ray diffraction analyses. Crystal Data: For 2: space group = P ($) over bar l, a = 10.782(1) Angstrom, b = 14.721(2) Angstrom, c = 9.940(2) Angstrom, alpha = 91.57(1)degrees, beta = 93.61(1)degrees, gamma = 70.774(9)degrees, Z = 4, 4516 reflections, R = 0.047 and for 5a: space group = P2(1)/n, a = 11.389(2) Angstrom, b = 9.660(2) Angstrom, c = 14.756(3) Angstrom, beta = 103.36(2)degrees, Z = 4, 1601 reflections, R = 0.022.