Co-ordination chemistry of higher oxidation states. Part 18. Bidentate selenoether complexes of the tetravalent platinum metals. Crystal and molecular structure of [Pt{o-C6H4(SeMe)2}Cl4]

Synthesis and characterisation of selenoether macrocyclic complexes of CoIII, RhIII and IrIII: crystal structures of trans-[CoBr2([16]aneSe4)]BPh4 and trans-[IrBr2([16]aneSe4)]BPh4([16]aneSe4= 1,5,9,13-tetraselenacyclohexadecane)

“…Reaction of anhydrous COX, (X = Cl, Br or I) with [16]aneSe, in MeNO, solution in air yields the cobalt(II1) selenoether cations [Cox,( [ 1 6]aneSe,)] + , which can be isolated as orange (X = C1 or Br) or purple (X = I) powders by addition of PF6-counter ion and diethyl ether. These complexes are stable in the solid state; the chloro and bromo species are also stable in MeNO, and MeCN solution, whereas [CoI,([l 6]aneSe,)]PF6 decomposes in MeCN solution over the course of a few minutes and in MeNO, solution over an hour or so.…”

“…Additionally, 77Se NMR spectroscopy (I = i, 7.8%) is a convenient probe through which to monitor the behaviour of Se-containing compounds in solution. In this context we have reported the preparation of the square-planar d8 species [M([l6]aneSe4)l2' (M = Pd or Pt; [16]aneSe, = 1,5,9,13tetraselenacyclohexadecane). 4 Treatment of [Pt( [16]-aneSe4)l2+ with X,-CCl, (X = C1 or Br) yields trans-[PtX,( [ 1 6]aneSe,)I2 +, the first examples of cationic platinum(1v) selenoethers.…”

“…In this context we have reported the preparation of the square-planar d8 species [M([l6]aneSe4)l2' (M = Pd or Pt; [16]aneSe, = 1,5,9,13tetraselenacyclohexadecane). 4 Treatment of [Pt( [16]-aneSe4)l2+ with X,-CCl, (X = C1 or Br) yields trans-[PtX,( [ 1 6]aneSe,)I2 +, the first examples of cationic platinum(1v) selenoethers. Platinum-195 and 77Se-{ 'H} NMR spectroscopic and X-ray crystallographic studies confirmed the Se,X, donor set in these octahedral species, and illustrate the ability of the soft selenoether macrocycle to stabilise the relatively hard platinum(1v) centre.…”

Selenium‐77 NMR of coordination compounds with unsaturated selenium ligands and/or selenium (II) central ions

“…The 77Se chemical shifts of K,i-mns (in D,O) and (Et,NH,)Et,dsc (in CDC1,)I3 differ by less than 60 ppm. In addition, the difference between the 'free ligand' K,i-mns (819.3 ppm) and its nickel (11) bis-complex [Ni(i-mns),]' -(642.6 ppm) on the one hand, and between (Et,NH,)Et,dsc (878.3 ppm) 13 and Ni(Et,dsc), (648.4 ppm)I3 on the other (176.7 and 229.9 ppm, respectively), agree fairly well, considering that the 77Se chemical shift range extends to more than 2500 pprn.' Comparison of R,tsc with i-mnts and their …”

Synthesis, properties, and multinuclear (1H, 13C, 77Se) magnetic resonance studies of the hybrid selenide ligands o-C6H4(SeMe)Y (Y = NMe2, PMe2, AsMe2, SbMe2, OMe, and SMe)

“…CloH1,IPSe requires C, 32.2; H, 4.3%). (3).-Sodium dimethylarsenide in T H F (200 cm3) was prepared from sodium wire (3.2 g, 0.14 mol) and iododimethylarsine (27.4 g, 0.12 rnol),, and was added dropwise to o-bromophenyl methyl selenide (30 g, 0.12 mol) in T H F (100 cm3). The mixture was stirred for 30 min, hydrolysed, and the organic phase separated and dried (Na,SO,).…”