Maribel Arroyo

Conversion of [Pt(SRf)2(PPh2 −n(C6F5)n+ 1)2](n= 0 or 1, RfC6HF4-4) through carbon–fluorine bond activation to [Pt(SRf)2(1,2-C6F4(SRf)-(PPh2))] and chiral [Pt(SRf)2(1,2-C6F4(SRf)(PPh(C6F5)))]

Treatment of trans-[PtCl(2)(PPh(2 - n)(C(6)F(5))(n + 1))(2)](n = 0 or 1) with Pb(SC(6)HF(4)-4)(2) yields a mixture of monometallic cis/trans [Pt(SC(6)HF(4)-4)(2)(PPh(2 - n)(C(6)F(5))(n + 1))(2)], thiolate-bridged bimetallic cis/trans [Pt(2)(mu-SC(6)HF(4)-4)(2)(SC(6)HF(4)-4)(2)(PPh(2 - n)(C(6)F(5))(n + 1))(2)] and [Pt(SC(6)HF(4)-4)(2)(1,2-C(6)F(4)(SC(6)HF(4)-4)(PPh(2 - n)(C(6)F(5))(n))].

CF bond activation in polyfluorobenzothiolate compounds of Os(III). X-ray structures of [-2))(SC6F5)2(PMe2Ph)2], [Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] and [Os(C6F5)2(o-S2C6F4)(PMe2Ph)2]

Abstract Thermolysis of [Os(SR) 3 (PMe 2 Ph) 2 ] (R=C 6 F 5 ( 1a ) or C 6 HF 4 -4 ( 1b )) in refluxing toluene affords [Os(SC 6 F 5 ) 2 ( o -S 2 C 6 F 4 )(PMe 2 Ph)] ( 2a ), [Os(SC 6 HF 4 ) 2 ( o -S 2 C 6 HF 3 )(PMe 2 Ph)] ( 2b ), and [Os(C 6 F 5 ) 2 ( o -S 2 C 6 F 4 )(PMe 2 Ph) 2 ] ( 3a ) through processes involving CF and CS bond cleavage as well as rearrangement of CS bonds. The single-crystal diffraction structures of 1a , 2a and 3a have been determined. In the solid state compound 1a shows a CF→Os interaction.

PREPARATION AND ELECTROCHEMISTRY OF THIOLATE-PHOSPHINE COMPLEXES OF OSMIUM

Abstract —The paramagnetic, octrahedral complexes [Os(SC 6 F 5 ) 2 (O 2 CR)(PMe 2 Ph) 2 ] (R = C 6 F 5 , 1; C 6 H 4 CF 3 -2, 2; C 6 H 4 CF 3 -3, 3; C 6 H 4 CF 3 -4, 4; C 6 H 4 F-2, 5; C 6 H 4 F-3, 6; C 6 H 4 F-4, 7 ; CH 3 , 8 ; CF 3 , 9) have been prepared by treatment of the penta-coordinated complex [Os(SC 6 F 5 ) 3 (PMe 2 Ph) 2 ] with the corresponding fluoro-carboxylic acid. The diamagnetic, pentacoordinate, osmium(IV) complexes [OsX(SR) 3 (PR 3 1 )] [X = Cl, Br or SR; R = C 6 F 4 H-4 or C 6 F 5 ; PR 3 1 = PMe 2 Ph, PPh 3 , P(C 6 H 4 Y-4) 3 (Y = F, OMe, CF 3 , Me or Cl)] (10–14, 18, 20–23), show two successive one-electron reductions. Electrochemical data are also given for [Os(SC 6 F 5 ) 3 (PMe 2 Ph) 2 ] (19).

Thiolate complexes of osmium(IV): preparation of [Os(SR)4(PR′3)](R = C6F5, C6F4H-4, C6H4F-4 or Ph, R′= Ph; R = C6F5 or C6F4H-4, R′3= Me2Ph) and [OsCl(SC6F5)2(SC6H4X-3)(PMe2Ph)](X = F or CF3): crystal structures of [Os(SC6F4H-4)4(PPh3)] and [OsCl(SC6F5)2(SC6H4CF3-3)(PMe2Ph)]

The diamagnetic osmium(IV) complexes [Os(SR)4(PR′3)](R = C6F5, C6F4H-4, C6H4F-4, or Ph, R′= Ph; R = C6F5 or C6F4H-4, R′3= Me2Ph) and [OsCl(SC6F5)2(SC6H4X-3)(PMe2Ph)](X = F or CF3) have been prepared. The complex [Os(SC6F4H-4)4(PPh3)] has an essentially trigonal-bipyramidal structure with an apical PPh3 group [Os–P 2.391 (5), Os–Sap 2.414(5), mean Os–Seq, 2.207(7)A]. The structure of [OsCl(SC6F5)2(SC6H4CF3-3)(PMe2Ph)] is a somewhat distorted triagonal bipyramid with apical Cl– and PMe2Ph groups [Os–Cl 2.420(2), Os–P 2.340(2), mean Os–SC6F5 2.206(2), Os–SC6H4CF32.187(2)A]. The spectroscopic properties of these compounds are reported and the possibility of isomerism in solution is discussed.

CF bond activation in perfluorobenzothiolate compounds of Os(III). X-ray structures of , [Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] and [Os(C6F5)2(o-S2C6F4)(PMe2Ph)2]

Thermolysis of (1) in refluxing toluene affords [Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] (2) and [Os(C6F5)2(o-S2C6F4)(PMe2Ph)2] (3) through a process involving CF cleavage as well as CS bond formation. The X-ray structures of 1, 2 and 3 have been determined. In the solid state compound 1 shows a CF → Os interaction.

Fluorothiolate–dithioacid complexes of ruthenium(III) and osmium(III): crystal structure of [Os(SC6F5)2(S2CNEt2)(PMe2Ph)2]

Treatment of the coordinative unsaturated complexes [M(SRF)3(PMe2Ph)2] (M = Os or Ru; RF = C6F5 or C6F4H-4) with M′S2Z (M′ = Na, S2Z = S2CNEt2; M′ = K, S2Z = S2COEt) and [Os(SRF)3(PMe2Ph)2] (RF = C6F5 or C6F4H-4) with M′S2Z [M′ = Na; S2Z = S2P(OEt)2] in Me2CO solution, gave the paramagnetic OsIII and RuIII derivatives, [M(SRF)2(S2Z)(PMe2Ph)2]. X-ray crystallography shows that [Os(SC6F5)2(S2CNEt2)(PMe2Ph)2] has an octahedral geometry with trans-fluorothiolates, cis-phosphines and a chelating N,N-diethyldithiocarbamate ligand.

Crystal structure of azido­(η5-cyclo­penta­dien­yl)bis­(tri­phenyl­phosphane-κP)ruthenium(II) di­chloro­methane hemisolvate

The title solvated complex, [Ru(η5-C5H5)(N3){P(C6H5)3}2]·0.5CH2Cl2, displays a typical piano-stool geometry about the RuII atom. The bond lengths and angles of the cyclopentadienyl and phosphane ligands are very similar to that of the unsolvated complex [Taqui Khan et al. (1994 ▶). Acta Cryst. C50, 502–504]. The azide anion displays similar N—N distances of 1.173 (3) and 1.156 (3) Å and has an N—N—Ru angle of 119.20 (15)°, indicating a greater contribution of the canonical form Ru—N=N(+)=N(-) for the bonding situation. An intramolecular C—H⋯N hydrogen-bonding interaction between one ortho H atom of a phosphane ligand and the N atom coordinating to the metal is observed. A similar intermolecular interaction is observed between a meta H atom of a phosphane ligand and the terminal azide N atom of a neighbouring complex. Finally, two C—H⋯N interactions exists between the H atoms of the dichloromethane solvent molecule and the terminal N atom of two azide anions. The solvent molecule is located about a twofold rotation axis and shows disorder of the Cl atoms with an occupancy ratio of 0.62 (3):0.38 (3).

Chloridotris(penta­fluoro­benzene­thiol­ato-κS)[tris­(4-fluoro­phen­yl)phosphine-κP]osmium(IV)

The title complex, [Os(C6F5S)3Cl(C18H12F3P)], displays a trigonal-bipyramidal OsIV coordination geometry with the S atoms of three thiolate ligands occupying the equatorial positions. The thiolate pentafluorophenyl substituents are all placed above the equatorial plane, forming a claw-like cavity which accommodates the chloride ligand with a normal Os—Cl bond length. The phosphine ligand trans to the chloride ligand reveals a short Os—P bond length compared to other chloride–phosphine OsIV complexes (average = 2.40 Å). This strong bonding indicates that the inductive effect of the F atoms in the phosphine does not affect significantly its basicity, compared to triphenylphosphine. This feature is also consistent with the known poor trans influence of Cl−. The crystal packing involves π–π contacts between inversion-related thiolate C6F5 rings, with a centroid–centroid separation of 3.659 (8) Å.

CF bond activation in perfluorobenzothiolate compounds of Os(III). X-ray structures of [Os(SC6F4(F-2))(SC6F5)2)(PMe2Ph2)], [Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] and [Os(C6F5)2(o-S2C6F4)(PMe2Ph)2]

Thermolysis of (1) in refluxing toluene affords [Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] (2) and [Os(C6F5)2(o-S2C6F4)(PMe2Ph)2] (3) through a process involving CF cleavage as well as CS bond formation. The X-ray structures of 1, 2 and 3 have been determined. In the solid state compound 1 shows a CF → Os interaction.

CF bond activation in perfluorobenzothiolate compounds of Os(III). X-ray structures of [Os(SC6F4(F-2))(SC6F5)2)(PMe2Ph2)], [Os(SC 6 F 5 ) 2 ( o -S 2 C 6 F 4 )(PMe 2 Ph)] and [Os(C 6 F 5 ) 2 ( o -S 2 C 6 F 4 )(PMe 2 Ph) 2 ]

Thermolysis of (1) in refluxing toluene affords [Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] (2) and [Os(C6F5)2(o-S2C6F4)(PMe2Ph)2] (3) through a process involving CF cleavage as well as CS bond formation. The X-ray structures of 1, 2 and 3 have been determined. In the solid state compound 1 shows a CF → Os interaction.