A facile, high-yield synthesis of [Pt₂(PR₃)₂(µ-Cl)₂Cl₂]

Abstract

A wide range of examples has been synthesised and fully characterised by "P-{lH} and 195Pt-{1H} spectroscopy. The dinuclear complexes [Pt,(PR3),(p-C1),Cl2] (R = alkyl or aryl)' are synthetically important as they are susceptible to cleavage of the chloro bridge by nucleophiles such as CO,, i m i n e ~, ~ amines,, o l e f i n ~, ~sulfoxides and thioethers allowing the formation of a wide range of mononuclear platinum(I1) derivatives. The primary method of synthesis of [Pt2(PR3)2(p-C1),Cl2] has been to reflux a slurry of [Pt(PR,),Cl,] and PtCl, in a mixture of xylene and naphthalene the ratio of which is varied in order to obtain the optimum reaction temperature.' Alternative solvents which have been recommended include tetrachloroethane and, more recently, p-chlorotoluene. The disadvantage of these methods is the necessity to use PtCl, which can be expensive as a source of platinum compared to [PtCl4l2 -, solutions of which are readily obtainable from platinum metal or platinum residues. l o Thus, we sought an alternative method for the synthesis of [Pt,(PR3)2(p-CI)2C12] that would employ [PtC1,I2-

Asymmetric Halogeno-Bridged Complexes of the Late Transition Metals − A Computational and Experimental Study

“…[27,46,48] An exception is the triphenylphosphane complex [(Ph 3 P)PtCl(µ-Cl)] 2 , for which the cis form can be isolated. [17] Two isomers were also found for the allyl complexes [(C 3 H 5 )M(µ-Cl)] 2 (M ϭ Pd, Pt): a planar trans isomer with a centre of symmetry and a cis form with a bent chloro bridge (Pt: θ ϭ 157.4°; Pd: θ ϭ 167.5°). The pairs of isomers are very similar in energy [∆E B3LYP (Pt cis/trans ) ϭ Ϫ2.60 kcal/mol; ∆E B3LYP (Pd cis/trans ) ϭ ϩ0.04 kcal/mol].…”

Experimental and theoretical vibrational spectroscopic study on symmetric and asymmetric halo‐bridged complexes of palladium(II) and platinum(II)

“…Experimentally, three bands have been observed in the infrared spectrum of cis-and trans-[(Ph 3 P)PtCl(µ-Cl)] 2 between 250 and 400 cm 1 . 32 The corresponding modes are very similar ( < 8 cm 1 ). The skeletal stretching wavenumbers of trans-[LMX(µ-X)] 2 complexes (M D Pt, Pd) have been investigated extensively by Goodfellow et al 34 and Taylor et al 35 Their findings are in agreement with our computational results.…”

“…3 An exception is the triphenylphosphine complex [(Ph 3 P)PtCl(µ-Cl)] 2 , for which the cis form can be isolated. 32,33 Halo-bridged complexes of the general formula cis-[LMX(µ-X)] 2 (M D Pt, Pd) possess C 2v symmetry, which can be decreased to C 2 , C s or C 1 by ligands such as PH 3 . The calculation was carried out in C 2v and C 2 symmetry.…”

Coordination Chemistry of Perhalogenated Cyclopentadienes and Alkynes, XXIX. The Reaction of Ni(0) and Pt(0) Phosphane Complexes with Trichloroethene, Hexachloro- and Hexabromocyclopentadiene

“…The small value of J (P-P) hints on a long range coupling, and therefore we assign these signals to the dimeric complexes cis-and trans-[Pt(PPh 3 )(Br)(µ-Br)] 2 , the NMR data of which apparently have not been reported. However, for the analogous chlorido-complexes (cis and trans) J PP = 5 Hz has been reported [26].…”