POLYNUCLEAR NITROSYL CARBONYL RE-I COMPLEXES WITH THIOLATE AND SULFIDE BRIDGES

The reaction of the complex Re-2(CO)(4)(NO)(2)Cl-4 (1) with NaSCMe3 (2 ) tin THF or MeCN, 65-80 degrees C, 24 h) was studied at different rat ios of the reagents (from 1 : 2 to 1 : 6). At the reagent ratio of 1 : 2, the binuclear complex Re-2(CO)(4)(NO)(2)Cl-2(mu-SCMe3)(2) (3) was obtained as a mixture of syn and anti isomers (3a and 3b, respectively ) containing Re2S2 fragments with different structures (the butterfly- like structure in 3a and the planar fragment in 3b). When the initials were taken in ratios from 1 : 4 to 1 : 6, two compounds were isolated : the binuclear complex Re-2(CO)(4)(NO)(2)(mu-SCMe3)(2)(mu-S) 4 (cocry stallized as a mixture of syn and anti isomers, 4a. and 4b, respective ly) and the triangular cluster Re-3(CO)(3)(NO)(3)(mu-SCMe3)(3)(mu(3)-S )(mu(3)-Cl) (5). Apparently, complex 4 is formed in the course of isol ation as a result of elimination of SR2 from the unstable tetrathiolat e dimer Re-2(CO)(4)(NO)(2)(SCMe3)2(mu-SCMe3)(2) (6). Cluster 5 is the product of the reaction between compounds 3 and 4. Products of interac tion of compound 6 with silica gel upon column chromatography of the r eaction mixture were studied. Four complexes containing hydroxy and ox o bridging groups, (CO)(2)(NO)Re(mu-SCMe3)(2)(mu-OH)Re(SCMe3)(CO) (NO) (7), )(3)(NO)(3)Re-3(mu-SCMe3)(3)(mu(3)-SCMe3)(mu(3)-O) (8), [(CO)(2) (NO)(2)Re-2(SCMe3)(2)(mu-SCMe3)(2)(mu-OH)] [Na(THF)(Et2O)] (9), and O) (2)(NO)(2)Re-2(SCMe3)(2)(mu-SCMe3)(2)(mu-OH](2)- [Na(H2O)(6)][H5O2] (1 0), were isolated. The structures of complexes 3, 4, 5, 7, 8, 9, and 1 0 were established by X-ray diffraction study.