Reactivity of Ph2P(O)py-2 with Platinum(II) Alkyl Derivatives − Building-up of a Chiral Phosphorus Atom through C,N-Cyclometallation

Abstract

The reaction of Ph 2 P(O)py-2 (HL) with methyl-and dimethylplatinum(II) derivatives afforded a series of six-membered C,N-cyclometallated species, [PtX(LЈ)(L)] (X=halide or Me; LЈ = neutral ligand, e.g. SMe 2 , SOMe 2 , CO, PAr 3 ) arising from activation of one C(sp 2 )−H bond of a phenyl substituent. The metallation entailed elimination of methane and caused the phosphorus atom to become chiral. The series includes the complex [Pt(Me)(CO)(L)] where the platinum atom is bonded to three different carbon atoms (C sp 3 , C sp 2 , C sp ). From

Bis(2,6-dinitroaryl)platinum(II) Complexes. Cis/Trans Isomerization

“…In the complex 2 cis , the geometry of the dimethyl sulfoxide moiety is virtually unaffected by S coordination and the S−O bond length (1.474(2) Å) is similar to that in solid dimethyl sulfoxide, determined at −60 °C (1.471(8) Å) . The Pt−S bond distance (2.2930(6) Å) lies in the range reported in other aryl Pt(II) complexes containing an S -dmso ligand bonded trans to an aryl group (2.2693(5)−2.324(2) Å), ,, but is longer than those in aryl Pt(II) complexes with an S -dmso ligand bonded trans to N , or O, as a consequence of the trans influence of an aryl group being stronger than that of a N or O donor ligand.…”

Unusual [Pt{κ2(C,N)}]+ → [Pt{κ2(N,N)}]+ Coordination Mode Flip of the Guanidinate(1−) Ligand in Cationic N,N′,N″-Tris(3,5-xylyl)guanidinatoplatinum(II) Bis(phosphine) Complexes. Syntheses, Structural and Theoretical Studies

“…The δ­( 31 P) shifts and 1 J P–Pt values observed for 10 – 15 and 18 compare favorably with the δ­( 31 P) shifts and 1 J P–Pt values reported for the six-membered cycloplatinated 2-benzylpyridine complex [Pt­{κ 2 ( C , N )}­{κ 2 (dppm)}]­[BF 4 ] and the six-membered cyloplatinated amine, 6-alkyl-2,2′-bipyridine, benzylpyridine, and pyridylphosphane oxide complexes of the type [Pt­{κ 2 ( C , N )}­{κ 2 (dppe)}]­[Cl], respectively. Platinacycles 19 and 20 revealed 31 P NMR spectral patterns analogous to those revealed by 13 – 15 ; however, δ­( 31 P) shifts are shifted less upfield in the former platinacycles.…”

“…The molar conductance (Λ M ) values of cationic platinacycles prepared in the present investigation fall in the range 68.4−116.0 Ω −1 cm 2 mol −1 (10 −3 M) anticipated for 1:1 electrolytes reported in the literature. 36 31 P NMR spectra of 10−15 revealed a pair of doublets with each doublet flanked by 195 The δ( 31 P) shifts and 1 J P−Pt values observed for 10−15 and 18 compare favorably with the δ( 31 P) shifts and 1 J P−Pt values reported for the six-membered cycloplatinated 2-benzylpyridine complex [Pt{κ 2 (C,N)}{κ 2 (dppm)}][BF 4 ] 38 and the sixmembered cyloplatinated amine, 27 6-alkyl-2,2′-bipyridine, 32 benzylpyridine, 38 and pyridylphosphane oxide 39 complexes of the type [Pt{κ 2 (C,N)}{κ 2 (dppe)}][Cl], respectively. Platinacycles 19 and 20 revealed 31 P NMR spectral patterns analogous to those revealed by 13−15; however, δ( 31 P) shifts are shifted less upfield in the former platinacycles.…”

Labile Pd-sulphur and Pt-sulphur bonds in organometallic palladium and platinum complexes [(COD)M(alkyl)(S-ligand)]n+—A speciation study

“…The Pt-S bond of 2.273(4) Å in [(COD)Pt(Me)(DMSO)][SbF 6 ] lies somewhat at the upper end of the scale for Pt-DMSO bonds which lie around 2.22 Å [94,95] Only for complexes with a strong donor ligand in the trans position is this value exceeded [93]. Interestingly, this includes other sulfoxide ligands [89,94].…”