Coordination chemistry of -: 31P NMR of rhodium, iridium and platinum complexes, and the crystal and molecular structures of >*CH2Cl2 and tBuNC)2>

Article abstract of DOI:10.1016/0022-328X(93)80367-K

Complexes of the anionic ligand, ^-, are readily prepared under mild conditions by reactions of CH(PPh2)(P(S)Ph2)2, in the presence of base (NHEt2), with chlorobridged complexes, , M = Rh or Ir, cod = cycloocta-1,5-diene, , and , MeOcod = 8-methoxy-cyclooct-4-ene-1-yl. The products are >, >, and > respectively, and the platinum complexes are both mixtures of the two possible isomers. Subsequent reactions of > with ^tBuNC followed by oxidative addition of I2 or benzyl bromide give tBuNC)2>, and isomeric mixtures of tBuNC)2> and tBuNC)2>. The complexes were characterized primarily by 31P nuclear magnetic resonance (NMR) studies and by two crystal structure determinations. Complex 1a, >*CH2Cl2 crystallized in the P2₁/c (No. 14) space group (Z = 4) with a = 12.294(3), b = 16.063(5), c = 21.384(5) Angstroem, β = 91.60(3) deg. Complex 4a(i), tBuNC)2> crystallizes in the (No. 114) space group (Z = 8) with a = b = 30.174(3), c = 11.317(2) Angstroem. Both complexes contain bidentate P,S bonded ligands with the second P=S group non-coordinated ( dangling ). In 1a, approximate square planar coordination about rhodium is completed by the two double bonds of a cod ligand, and in 4a(i), the P,S ligand and two cis iodides comprise the equatorial plane of an octahedron which is completed by two ^tBuNC ligands.