Synthesis and Properties of Organometallic Pt^II and Pt^IV Complexes with Acyclic Selenoether and Telluroether Ligands and Selenoether Macrocycles

Abstract

The first series of planar dimethyl(selenoether)Pt II complexes, [

Structural Variation in [PdX2{RE(CH2)nNMe2}] (E = Se, Te; X = Cl, OAc) Complexes: Experimental Results, Computational Analysis, and Catalytic Activity in Suzuki Coupling Reactions

“…The two dl forms IV and VI are identical by rotation. The pyramidal inversion at the sulfur, selenium, and tellurium center in mononuclear complexes trans ‐[MX 2 (ER 2 )] (M = Pd, Pt; X = Cl, Br; R = Et,23 CH 2 SiMe 3 24) and trans ‐[MX 2 {RE(CH 2 ) 3 ER}] (X = Cl, Me; R = Me,25 Ph26) has been reported to generate invertomers. For selenoether complex 2d , the monomeric form predominates, whereas for telluroether ligands, all three structural forms of 2e and 2f exist with nearly equal probability.…”

Selenoether macrocyclic chemistry–syntheses and ligand properties of new small-ring Se3- and Se2N-donor macrocycles

“…26 We have also reported a series of related Pt(IV) complexes with di-, tri-and tetra-selenoether ligands. 12 Hence there is a significant volume of data is available for comparison with the new macrocyclic species Table 4, and although for L = L 1 and L 3 the complexes are dynamic at 298 K (probably due to reversible dissociation or 'ringwhizzing'), cooling the solutions to 233 K slows the dynamic process(es) sufficiently so that the δ Se resonances are clearly evident, and the observation of PtSe coupling on all of these (only one for L = L 2 ) strongly suggests the κ 3 -coordination mode. The coordination shifts (∆ Se = δ Se (complex) − δ Se (ligand)) ( microanalyses, magnetic and spectroscopic data.…”

“…12 The nature of the linking groups between the macrocyclic donor atoms in L 1 −L 5 allows, on one hand, the overall ring size to be controlled, while also clearly influencing to some extent the donor properties and solution dynamics of the complexes.…”

“…2,3,5 Synthetic routes to tetraselena-and hexaselena crowns were originally reported by Pinto et al [6][7][8] and the coordination chemistry of especially [16]aneSe 4 (1,5,9,13-tetraselenacyclohexadecane) and to a lesser extent [24]aneSe 6 (1,5,9,13,17,21-hexaselenacyclotetracosane) have been developed with both d-block and p-block elements. 5,[9][10][11][12] The macrocyclic framework facilitates stabilization of unusual species such as [CrX 2 ([16]aneSe 4 )]PF 6 (X = Cl, Br or I), [NiX 2 ([16]aneSe 4 )] containing the hard, oxo-philic d 3 Cr(III) and labile d 8 Ni(II) ions respectively, 9,10 within a selenium-rich coordination environment, and trans-[PtX 2 ([16]aneSe 4 )](PF 6 ) 2 (X = Cl or Br) based upon distorted octahedral Se 4 X 2 coordinated Pt(IV). 11 The only known examples of Se 3 macrocycles are [12]aneSe 3 , 13 a naphthyl based Se 3 -donor ring 14 and Me 6 [12]aneSe 3 , 15 the latter obtained via catalytic cyclooligomerisation of 3,3-dimethylselenetane using rhenium carbonyl species.…”

“…5,[9][10][11][12] The macrocyclic framework facilitates stabilization of unusual species such as [CrX 2 ([16]aneSe 4 )]PF 6 (X = Cl, Br or I), [NiX 2 ([16]aneSe 4 )] containing the hard, oxo-philic d 3 Cr(III) and labile d 8 Ni(II) ions respectively, 9,10 within a selenium-rich coordination environment, and trans-[PtX 2 ([16]aneSe 4 )](PF 6 ) 2 (X = Cl or Br) based upon distorted octahedral Se 4 X 2 coordinated Pt(IV). 11 The only known examples of Se 3 macrocycles are [12]aneSe 3 , 13 a naphthyl based Se 3 -donor ring 14 and Me 6 [12]aneSe 3 , 15 the latter obtained via catalytic cyclooligomerisation of 3,3-dimethylselenetane using rhenium carbonyl species. Recently we have reported routes to tridentate mixed S/Te macrocycles and tridentate and hexadentate O/Te and O/Se macrocyclic ligands.…”