THE CHEMISTRY OF PYRIDINE THIOLS AND RELATED LIGANDS, PART 6 - THE CRYSTAL AND MOLECULAR-STRUCTURE OF NO)PROPANE][BIS(PYRIDINE-2-THIOLATO)]RUTHENIUM(II) - A COMPARISON WITH SOLUTION-PHASE BEHAVIOR

Reaction of cis-RuCl2(dppp)(2) with pyridine-2-thiol (HpyS) in the pre sence of Et3N in dry benzene replaces both the chloro groups and a dip hosphine molecule to form Ru(dppp)(pyS)(2) (1) [dppp = Ph2P(CH2)(3)PPh 2], whose crystal and molecular structure has been determined with the help of single crystal X-ray crystallography. The discrete molecules of (1) adopt a distorted octahedral structure containing chelating pyr idine-2-thiolato and dppp ligands with trans-S, cis-N and cis-P atom d ispositions. The important interatomic parameters are: Ru-S, 2.443(2), 2.339(2); Ru-N, 2.133(5), 2.129(5); Ru-P, 2.274(2), 2.279(2) Angstrom ; trans-bond angles, S-Ru-S, 153.89(6); N-Ru-P, 172.76(13), 163.51(14) degrees; bite angles: P-Ru-P, 90.71(6); 1 N-Ru-S, 67.18(14), 67.72(14) degrees. The n.m.r. spectra (H-1, C-13, P-31) of (1) are also reported in order to compare solution phase behaviour with the solid state str ucture. The C-13-n.m.r. spectrum of the complex shows the presence of non-equivalent phenyls in the Ph2P-moiety.