Diana Cruz-Garritz

RuX = C (X F or H) interactions in complex compounds. Preparation and crystal structures of [RuSC6F4(F-2) (SC6F5)2(PMe2Ph)2] and [Ru(SC6F5)2PC6H4(H-2)(C6H5)22]

The diamagnetic complex [Ru(SR)2(PPh3)2] and the paramagnetic compounds [Ru(SR)3(PR′3)2] (R = C6F5, C6F4H, C6FH4, or C6H5; PR′3 = PPh3, PMe2Ph or PEt2Ph) have been prepared by treatment of [RuCl2(PPh3)3] or [RuCl3(PR′3)3]. respectively, with [Pb(SR)2] in acetone or tetrahydrofuran. An X-ray diFfraction study on [Ru(SC6F5)2PC6H4(H-2)(C6H5)22] has revealed a pseudo-octahedral structure, apparently with two CHRu interactions. The complexes [Ru(SR)3(PR′3)2] have μeff in the range 1.8–1.9 BM and EPR spectra are reported. An X-ray study of [RuSC6F4(F-2)(SC6F5)2(PMe2Ph)2] has shown that it has essentially octahedral geometry, involving a CFRu interaction.

Polyfluorothiolate derivatives of rhodium(I). Crystal and molecular structure of [Rh(μ-SC6HF4)(C8H12)]2

SummaryThe thiolato-bridged dinuclear compounds [Rh(μ-SR)-(COD)]2, where R=p-C6HF4 (1),p-C6H4F (2) and CF3 (3), are obtained from the chloro-bridged analogue by ligand exchange.Compound (1) crystallizes in the space group P1 with a=9.740(3)Å, b=11.642(4)Å, c=13.997(6)Å, α=103.87(3)°, β=106.98(3)° and γ=105.10(2)°; z=2. In this dinuclear molecule both Rh atoms have a square planar coordination sharing one edge, namely the two sulphur bridging atoms. The Rh—Rh separation of 2.96 Å is consistent with at most a very weak metal-metal interaction. Upon addition of CO the dimeric [Rh(μ-SR)(CO)2]2 (4), (5) and (6) are obtained, but addition of PPh3 affords the monomeric species [Rh(SR)(PPh3)-(COD)] (7), (8) and (9). Reactions of the dimeric tetracarbonyl derivatives with PPh3 vary with the nature of R; [Rh(μ-SR)(PPh3)(CO)]2 is obtained when R=p-C6H4F (10) and CF3 (11) but monomeric [Rh(SR)-(PPh3)(CO)2] (12) is produced when R=p-C6HF4. The latter mononuclear compounds, with R=p-C6H4F (13) and CF3 (14), are also formed by reaction of [Rh(SR)-(PPh3)(COD)] with CO.

A C–F–Ru interaction in a complex: preparation and X-ray structure of [Ru{SC6F4(F-2)}(SC6F5)2(PMe2Ph)2]

Treatment of [RuCl3(PMe2Ph)2] with Pb(SC6F5)2 in acetone gives [[graphic omitted]-2)}(SC6F5)2(PMe2Ph)2] whose X-ray structure shows a C–F–Ru interaction.

Preparation and properties of the dicarbonyl-thiolate complexes [Ru(SR)2(CO)2(PR′3)2]

Abstract The preparations of the complexes [Ru(SR) 2 (CO) 2 (PR′ 3 2 ] (R  C 6 F 5 , C 6 F 4 H, C 6 FH 4 , C 6 H 5 , CH 3 or Bu t ; PR′ 3  PMe 2 Ph or PPh 3 ) are described, together with spectroscopic data used to assign configurations.

Pentafluorothiophenolate Derivatives of Cobalt(ii) and Nickel(ii) - the Molecular-structure of [ni(sc6f5)2ph2pch2ch2pph2]

SummaryThe tetrahedral compounds [Co(SC6F5)2L] (L=Ph2P(CH2)nPPh2,n=1, 2 and 3) and the squareplanar compound [Ni(SC6F5)2(PhPCH2CH2PPh2)] have been obtained by mathematical reactions of [MX2L] (M=Co or Ni, X=Cl or Br) and Pb(SC6F5)2. The reaction of pentacoordinate [CoCl(Ph2PCH2CH2PPh2)2]+ and the lead salt yields [CoCl2L] and [Co(SC6F5)2L]. Magnetic moments, u.v. data (both in solution and solid state) and the crystal and molecular structure of the nickel compound are reported.

Polythiolated complexes. Part 2(1). Palladium(II) and platinum(II) derivatives of polyfluorophenylthiolates

SummaryThe preparation and characterization of the new thiolate complexes [M(SR)2(SEt2)2] (M=Pt, R=C6F5 orp-C6HF4) and [M(SR)2]n (M=Pd, R=C6F5,p-C6HF4 orp-C6H4F; M=Pt, R=p-C6H4F) is discussed. The tendency to form polymeric, rather than monomeric species, varies as follows: Pd>Pt; C6H4F>C6HF4> C6F5. [Pt(SC6F5)2(SEt2)2] has atrans square planar coordination.

The preparation and X-ray crystal structure of [Ru(SC6F52{P(C6H5)2(H4C6H-2)}2]

Abstract The complex [Ru(SC 6 F 5 ) 2 (PPh 3 ) 2 ] has been prepared from [RuCl 2 (PPh 3 ) 3 ] and [Pb(SC 6 F 5 ) 2 ] and shown by X-rays to have a pseudo-octahedral structure apparently with two RuHC interactions. It reacts with CO to give [Ru(SC 6 F 5 ) 2 -(CO) 2 (PPh 3 ) 2 ].

Thiolate complexes of osmium(III) and osmium(IV). Crystal structures of [Os(SC6F5)2(O2CPh)(PMe2Ph)2] and [OsCl-(SC6F5)3(PMe2Ph)]

Treatment of [Os(SR)3(PMe2Ph)2](R = C6F5 or C6HF4) with PhCO2H or with HCl in acetone gives, respectively, the red paramagnetic osmium(III) derivatives [Os(SR)2(O2CPh)(PMe2Ph)2]1 and the green, five-co-ordinate, diamagnetic osmium(IV) complexes [OsCl(SR)3(PMe2Ph)]2. X-Ray crystallography has shown that 1(R = C6F5) has an octahedral structure with trans-thiolates, cis-phosphines and a chelating benzoate ligand and that 2(R = C6F5) has a trigonal-bipyramidal structure with thiolates in the equatorial plane.

Thiolate complexes of osmium(III) with tertiary phosphines and their dicarbonyl derivatives of osmium(II): X-ray crystal structure of trans,trans,trans-[Os(SC6F5)2(CO)2(PEt2Ph)2]

The preparation and physical properties of complexes of the type [Os(SC6F5)3(PR3)2] and [Os(SC6F5)2(CO)2(PR3)2](PR3= PMe2Ph, PMePh2, PEt2Ph, or PEtPh2), and the X-ray structure of trans,trans,trans-[Os(SC6F5)2(CO)2(PEt2Ph)2] are described.

Dinitrogen complexes of osmium(II) with thiolate co-ligands: X-ray structure of mer-[OsCl(SC6F5)(N2)(PMe2Ph)3]

Treatment of mer-[OsCl2(N2)(PMe2Ph)3] with S2CNMe2– salts causes loss of N2 and the formation of mer/fac-[OsCl(S2CNMe2)(PMe2Ph)3] and cis-[Os(S2CNMe2)2(PMe2Ph)2]. Dinitrogen is, however, retained in reactions of mer-[OsX2(N2)(PMe2Ph)3](X = Cl or Br) with RS–(R = Ph, C6F5, Me, or CF3) at 20 °C in acetone to give the series mer-[OsX(SR)(N2)(PMe2Ph)3]. Under more vigorous conditions the N2 is displaced by thiolate. The compound mer-[OsCl(SC6F5)(N2)(PMe2Ph)3] has an octahedral structure with N2trans to chloride; d(N–N)= 1.112(5)A and d(Os–S)= 2.507(1)A.