Reaction of 3,3,5,5‐Tetraphenyl‐1,2,4‐trithiolane with Pt⁰(bisphosphane)(η²‐nbe) Complexes Bearing Bridged Bisphosphane Ligands with Various Bite Angles

Abstract

Keywords: P ligands / S ligands / Rearrangement / Thiosulfines / PlatinumA series of Pt 0 (η 2 -nbe) complexes [nbe = norbornene (bicyclo[2.2.1]hept-2-ene)] bearing bridged bisphosphane ligands with various bite angles (5a-c) was treated with 3,3,5,5-tetraphenyl-1,2,4-trithiolane (1) at 50°C in a toluene solution. These reactions resulted in the formation of the appropriate dithiolato complexes 6a-c as well as the η 2 -thioketone complexes 7a-c with respect to the 31 P{ 1 H} NMR spectroscopic data. All isolated complexes were fully characterized. Kinetic investigations using 31 P{ 1 H} NMR spectroscopy revealed

Reversible CO exchange at platinum(0). An example of similar complex properties produced by ligands with very different stereoelectronic characteristics

“…There are currently 12 Pt and 26 Pd xylenediyl diphos chelates in the Cambridge Crystallographic Database (CSD) 22 , 35 of which have structures where the two M-P-C-C(Ph) torsion angles have similar absolute values and the ring conformation is half-chair-like with an essentially coplanar MP 2 C 2 component as depicted as A in Chart 2. In the remaining 3 structures (HUXCIN, 23 HUXCEJ 23 and IHETOF 24 ) the chelate rings adopt a twist-boat-like conformation, with two different Pt-P-C-C(Ph) torsion angles of approximately ±50°and ±14°. The conformation of the Pt-L a ring in 5a (see Fig.…”

Sulfoxygenation of Active Site Models of [NiFe] and [FeFe] Hydrogenases – A Commentary on Possible Chemical Models of Hydrogenase Enzyme Oxygen Sensitivity

“…. [67][68][69][70]72,73] The latter complex offered the opportunity to observe S-oxygenation distributions for the thioether bridgehead sulfur atoms vs. the μ-thiolate sulfur atoms. With DMD as oxygen atom source, all levels of S-O products shown in Figure 12 were realized with maximum yields obtained for 7a (98 % when reacted with 1 equiv.…”

Synthesis of ligands based on naphthalene peri-substituted by Group 15 and 16 elements and their coordination chemistry

“…Heating the same compounds in toluene under reflux gives another tetranuclear complex (22), with both Ph groups having been detached from one of the phosphorus atoms.…”

“…Reactions of norbornene complex 11 [20][21][22]. with square planar geometry at the Pd atom (Scheme 6) [19].…”

“…Whilst the platinum species 10a was isolated in the crystalline state, only solution NMR data are presented for the palladium complex 10b, and no characterisation data are available for nickel complex 10c due to fast decomposition of the complex at room temperature [16]. Notably, the norbornene complex 11 is suggested as an easily accessible and clean source of [dppnPt(0)], a 14 electron complex [20], and as such has been used in the insertion and other reactions shown in Scheme 5 [20][21][22].…”