Hugo Torrens

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.

Catalytic activity of some fluorothiolate derivatives of rhodium(I). Crystal structure of [Rh(μ-SC6H4F)(CO)2]2

Abstract The thiolato-bridged dinuclear compounds [Rh(μ-L)(CO)2]2, L = SC6F5 (1), p-SC6HF4 (2) and p-SC6H4F (3) have been obtained from the corresponding chloride-bridged species by reactions with the lead thiolates Pb(L)2. Compound 3 crystallizes in the space group P21/a with a = 17.2722(6), b = 8.9804(2), c = 25.1874(12) A, β = 102.741(3)°, Z = 8. The values of the dihedral angles, 115.3(1) and 114.3(1)°, between the two coordination planes SRhS, for both molecules point to a “bent” geometry with intermetallic RhRh distances of 3.076(2) and 3.070(2) A, which are consistent with assumed absence of metalmetal bonding. The [Rh(μ-L)(CO)2]2/nPPh3 systems involving 1 to 3 or the corresponding complex with L = SCF3 (4) have been studied as catalyst precursors for the hydroformylation of 1-hexene in dichloroethane at 5 bar and 30°C. The extent of aldehyde conversion ranges from 5 to 94%, with selectivities towards linear relative to branched aldehydes in the range 3 to 3.5.

Pentafluorobenzenethiolato derivatives of the platinum group metals

Abstract Coordination chemistry involving fluorinated thiolates is an area of great current interest. This review is focused on the pentafluorobenzenethiolate ion [(SC 6 F 5 ) − ] derivatives of the platinum group metals. For each pair of metallic centres—Ru, Os; Rh, Ir; Pd, Pt—a literature survey brings together the known compounds and their relevant data, whereas recent selected results, particularly those from our group, are discussed. The chemical richness of this area is exemplified through some specific compounds of special interest such as [Ru(SC 6 F 5 ) 2 (PMe 2 Ph) 2 , as a stable example of a 14-electron compound bearing two C–H–Ru agostic bonds; [Os(SC 6 F 5 ) 2 (PMe 2 Ph) 3 ], with a rare trigonal-bipyramidal geometry in the solid state; [Cp*Rh(μ-SC 6 F 5 ) 3 RhCp*][Cp*Rh(SC 6 F 5 ) 3 ] which undergo an unusual rearrangement in solution; [Ir 3 (μ-SC 6 F 5 ) 3 (μ-CO)(CO) 3 (PPh) 3 ], a trimetallic compound bearing an Ir 3 (μ-SC 6 F 5 ) 3 skeleton; [Pd 2 (μ-SC 6 F 5 ) 2 (η 3 -C 3 H 5 ) 2 ], with an interesting fluxional behaviour involving rotating allyl moieties and inversion at the sulfur atoms and [(SC 6 F 5 ) 2 Pt(μ-SC 6 F 5 ) 2 Pt(SC 6 F 5 ) 2 ], which is a fully fluorinated, homoleptic platinum complex.

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))].

Allyl–palladium compounds with fluorinated benzenethiolate ligands. X-ray crystal structure of [(η3-C3H5)Pd(μ-SC6H4F-4)2Pd(η3-C3H5)]

Abstract Treatment of the di-μ-chloride allyl–palladium complex [(η3-C3H5)Pd(μ-Cl)2Pd(η3-C3H5)] with Pb(SR)2 in acetone affords dinuclear fluorothiolate bridged complexes of the type [(η3-C3H5)Pd(μ-SR)2Pd(η3-C3H5)] (R=C6F5, 1; C6HF4-4, 2; C6H4F-2, 3; C6H4F-3, 4 and C6H4F-4, 5). Complex 1 reacts with para-substituted phosphines P(C6H4X-4)3 to give the mononuclear perfluorobenzenethiolate complexes [Pd(SC6F5)(η3-C3H5)(P(C6H4X-4)3)] (X=F, 6; CF3, 7; OCH3, 8 and CH3, 9). The single crystal X-ray diffraction structure of [(η3-C3H5)Pd(μ-SC6H4F-4)2Pd(η3-C3H5)] (5) has been resolved.

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.

Allyl–palladium complexes with fluorinated benzene thiolate ligands. Examination of the electronic effects in the Pd-catalyzed allylic alkylation reaction with the catalytic system [(η3-C3H5)Pd(μ-SRf)]2/PR3

Abstract The bimetallic complexes [(η 3 -C 3 H 5 )Pd(μ-SR f )] 2 [R f =C 6 F 5 , ( 1 ); C 6 F 4 H-4, ( 2 ); C 6 H 4 F-2, ( 3 ); C 6 H 4 F-3, ( 4 ) and C 6 H 4 F-4, ( 5 )] in the presence of para -substituted phosphines P(C 6 H 4 X-4) 3 [X=OCH 3 , CH 3 , H, F, Cl, and CF 3 ] are efficient catalytic systems in the allylic alkylation couplings of ( E )-3-acetoxy-1,3-diphenyl-1-propene and dimethyl malonate. Results concerning the electronic effects of both sulfur and phosphorus substituents in this reaction are discussed.

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.

Pentafluorophenylthiolate derivatives of ruthenium(II), rhodium(I) and palladium(II)

SummaryThe pentafluorophenylthiolate anion [C6F5S]− reacts with chloro-bridged binuclear complexes of RuII, RhI and PdII to give the compounds [(N-N)(PPh3)2Ru(SC6F5)]2Cl2 (1) (N-N = bipyridine), [LRh(SC6F5)]n (L = cycloocta-1,5-diene (2) or norbornadiene (3), n = 2 and L = dicyclopentadiene (4) for which n is probably 4), [(PPh3)Pd(SC6F5)Cl]2 (5) and (MeS-CHMeCHMeSMe)Pd(SC6F5), (6).19F n.m.r. spectroscopy shows a variable number of isomers depending on the compound considered.

Synthesis of neutral rhenium(V) complexes with fluorinated benzenethiols: the crystal and molecular structure of [ReO(C6H4S-2-F)3(PPh3)]

Abstract The complexes [ReO(SRf)3(PPh3)] and [ReN(SRf)2(PPh3)2] [Rf=C6F5 (1) and (6), C6F4-4-H (2) and (7), C6H4-2-F (3) and (8), C6H4-3-F (4) and (9) and C6H4-4-F (5) and (10)] were synthesized in good yields by reacting [ReOCl3(PPh3)2] or [ReNCl2(PPh3)2] and the lead salt of the corresponding fluorobenzenethiol [Pb(SRf)2]. In contrast, when the free thiol HSC6F5 was employed in the presence of NEt3 as base, the ionic species [ReO(SC6F5)4][NEt3·HCl] (11) was isolated. The X-ray crystal structure of 3 was determined.