Heteropolytopic phosphanylarylthiolato ligands: formation of cis isomers of nickel(ii), palladium(ii) and platinum(ii) complexes with 1-P(Biph)-2-SHC6H4 (Biph = 1,1′-biphenyl-2,2′-diyl)

Abstract

Reaction of the ditopic phosphanylarylthiol 1-P(Biph)-2-SHC(6)H(4) (BiphPSH, Biph = 1,1'-biphenyl-2,2'-diyl), prepared by lithiation-electrophilic substitution, with NiCl(2)·6H(2)O, Na(2)[PdCl(4)] and [PtI(2)(cod)] (cod = 1,5-cyclooctadiene) in a 2:1 ratio and in the presence of NEt(3) led to formation of exclusively cis isomers of the square-planar complexes cis-[M{(1-P(Biph)-2-S-C(6)H(4))-κ(2)S,P}(2)] ([M{(BiphPS)-κ(2)S,P}(2)]; M = Ni (1), Pd (2), Pt (3)). Density functional calculations support the assumption that this is probably due to intramolecular π-π interaction of the biphenyl groups, which results in enhanced stability of the cis isomers. Compound 1 is the first example of a structurally characterised mononuclear cis-bis(phosphanylthiolato)nickel(III) complex. Small amounts of the trinuclear complex [{PtI(1-P(Biph)-μ-2-S-C(6)H(4)-κ(2)S,P)}(3)] (4) are also formed besides the mononuclear platinum bis-chelate complex 3.

Tuning the coordination properties of phenothiazine by regioselective introduction of diphenylphosphanyl groups

“…The C-P coupling constants ( 1 J PC = 5.6-10.9 Hz; 2 J PC = 17.9-30.8 Hz; 3 J PC = 5.7-8.9 Hz) have values similar to those of other phosphorusaryl containing compounds. 16 The electronic properties of phenothiazinyl-phosphines 1, 3 and 4 were investigated by absorption/emission UV/Vis spectroscopy and cyclic voltammetry. UV absorption and emission data of dilute solutions are listed in Table 1.…”

Reaction of a heterotopic P,SAs ligand with group 10 metal(ii) complexes: As–S bond cleavage and the formation of two unusual trinuclear structural isomers for Pd and Pt

“…The structures of several trinuclear platinum 3,21-23 and palladium 24,25 complexes with bridging sulfur atoms have been described, but none of them contain the (SC 25 and in [PtI{(μ-S-SC 6 H 4 -2-AsPh 2 )-κ 2 S,As}] 3 3 and [PtI{(μ-S-SC 6 H 4 -2-P(Biph)}-κ 2 S,P}] 3 (Biph = 1,1′-biphenyl). 23 However, the distortion of the ring is more pronounced in [PtI{(μ-S-SC 6 H 4 -2-P(Biph))-κ 2 S,P}] 3 due to the greater rigidity introduced by the biphenyl groups.…”

“…Rearrangement to the more stable trimeric form, the final thermodynamic products 2 and 4, occurs over about three weeks at room temperature in THF (Scheme 2B). The formation of trans- 3,23 Due to the continuous interconversion of the metal complexes and their poor solubility in common solvents, their separation in a pure form proved to be very difficult and prevented the recording of 13 C{ 1 H} NMR spectra.…”

Structural Preferences in Phosphanylthiolato Platinum(II) Complexes

“…This cycle adopts a skew‐boat conformation (Figure ) with each bridging sulfur atom showing one shorter and one longer Pt−S bond (Figure ). Similar unsymmetrical bridging sulfurs were observed in related compounds . The S−Pt−S angles are smaller than Pt−S−Pt ones because of the restriction imposed by the metal square‐planar coordination.…”

“…The crystal structure reveals a sulfur‐bridging edge‐sharing cyclic trinuclear complex with square‐planar coordination geometry around the platinum atoms (Figure ). Related structures were found for aminoalkylthiolato, [PtBr(μ‐SCH 2 CH 2 NMe 2 ‐κ 2 N , S )] 3 , phosphanylarylthiolato, [PtI(μ‐SC 6 H 4 ‐2‐PPh 2 ‐κ 2 P , S )] 3 and [PtI{μ‐SC 6 H 4 ‐2‐P(1,1′‐biphenyl)‐κ 2 P , S }] 3, and arsanylarylthiolato ligands, [PtI(μ‐SC 6 H 4 ‐2‐PAs 2 ‐κ 2 As , S )] 3 , but complex 2 is, to our knowledge, the first example with phosphanylalkylthiolato ligand.…”