Metal–heterocyclic thione interactions. 13. Pyridine-2-thione derivatives of copper(I): crystal structure of dinuclear [bromo(pyridine-2-thione)(tri-p-tolylphosphine)copper(I)]2 complex

Metal–heterocyclic thione interactions.

Structural characterization and investigation of iron(III) complexes with nitrogen and phosphorus based ligands in atom transfer radical addition (ATRA)

Reaction of cis-RuCl2(dppp)2 with pyridine-2–thiol (HpyS) in the presence of Et3N in dry benzene replaces both the chloro groups and a diphosphine molecule to form Ru(dppp)(pyS)2 (1) [dppp=Ph2P(CH2)3PPh2], 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 pyridine-2–thiolato and dppp ligands with trans-S, cis-N and cis-P atom dispositions. 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)A; trans-bond angles, S-Ru-S, 153.89(6); N-Ru-P, 172.76(13), 163.51(14)°; bite angles: P-Ru-P, 90.71(6); N-Ru-S, 67.18(14), 67.72(14)°. The n.m.r. spectra (1H, 13C, 31P) of (1) are also reported in order to compare solution phase behaviour with the solid state structure. The 13C-n.m.r. spectrum of the complex shows the presence of non-equivalent phenyls in the Ph2P-moiety.

The chemistry of pyridine thiols and related ligands, Part 6. The crystal and molecular structure of (1,3-bis(diphenylphosphino)- propane)(bis(pyridine-2-thiolato))ruthenium(II). A comparison with solution phase behaviour

Formation of two stable seven-membered chelate rings bound to one metal center due to addition of bifunctional amine to coordinated nitriles

Attempts to prepare the mixed ligand complex, FeCl2(pyS)(Ph3P)2 from the reaction of iron(III) chloride with 2(1H)-pyridinethione-S(HpyS) and triphenylphosphine(Ph3P) in ethanol instead formed FeCl2(HPyS)2 characterized by X-ray crystallography. The structure was determined by the heavy atom method, using MoKα diffractometer data, and refined by full-matrix least squares toR=0.049 for 1123 observed reflections. The molecule possesses twofold symmetry with a distorted tetrahedral geometry about the iron(II) center with S-Fe-S and Cl-Fe-Cl bond angles of 98.76(5)° and 115.79(5)° and Fe-S and Fe-Cl bond distances 2.345(1) A and 2.288(1) A, respectively. Hydrogen bonding between NH and chlorine atoms leads to a polymeric type structure of linked molecules running approximately parallel to thea axis.

X-ray crystal and molecular structure of dichlorobis [2(1H)-pyridinethione-S]iron(II)

Reaction of iron(III) chloride with 1,2-ethanebis(diphenylphosphine oxide) in an ethanol/chloroform mixture formed a 1∶1 adduct of stoichiometry FeCl3(L-L) which has been characterized by X-ray crystallography as [FeCl2(L-L)2] [FeCl4]. The structure was solved by the heavy atom method, using MoKα diffractometer data and refined by full-matrix least squares toR=0.044 for 8506 observed reflections. The coordination is slightly distorted octahedral for the cation with acis-arrangement of the chlorine atoms and a seven-membered chelate ring formation by Ph2P(O)CH2CH2P(O)Ph2 with the donor O atoms also in acis arrangement. The Fe-Cl distances are equal at 2.306(1) A but the Fe-O distances differ significantly in each of the two ligands, (avg. 2.076(2) A; avg. 1.975(3) A).

X-ray crystal and molecular structure of cis-dichlorobis[1,2-ethanebis(diphenylphosphineoxide)] iron(III)tetrachloroferrate(III), [FeCl2(L-L)2] [FeCl4]

P. K. Bhatia

Papers

X-ray crystal and molecular structure of dichlorobis [2(1H)-pyridinethione-S]iron(II)

X-ray crystal and molecular structure of cis-dichlorobis[1,2-ethanebis(diphenylphosphineoxide)] iron(III)tetrachloroferrate(III), [FeCl2(L-L)2] [FeCl4]