Osmium(II) and Osmium(IV) Complexes with Phosphane–Ethers, –Esters, and –Amines as Mono‐ and Bidentate Ligands

Abstract

, 8), which were also obtained on heating the osmium(IV) precursor 3 or the labile 1:1 adducts of 3 and 4 with ethene in benzene under reflux. The dihydrido compounds 2 and 3 reacted with CO at room temperature to give initially the octahedral all-cis-configured complexes [OsCl 2 (CO) 2 {κ(P)-iPr 2 PCH 2 CH 2 OMe} 2 ] (11a) and [OsCl 2 (CO) 2 {κ(P)-iPr 2 PCH 2 CO 2 Me} 2 ] (12a), which rearrange to the more stable cis,cis,trans isomers 11b and 12b in benzene under reflux. The all-trans isomer 11c and the monocarbonyl complexes trans,trans-[OsCl 2 (CO){κ 2 (P,O)-

Bis(pyridylimino)isoindolato (BPI) Osmium Complexes: Structural Chemistry and Reactivity

“…The vinylidene ligand coordinates to the osmium atom in a nearly linear fashion with a bond angle Os–C(29)–C(30) of 176.1°. The Os–C(29) and C(29)–C(39) bond lengths are 1.867 and 1.321 Å, respectively, and agree well with those found in other osmium vinylidene complexes. ,, …”

Oxidation of Aniline with Sulfate Radicals in the Presence of Citric Acid

“…To overcome this limitation, a chelant is applied to increase Fe 2þ solubility. Since, according to ASTM-A-380, chelating agents or chelating agents are chemicals that form soluble, complex molecules with certain metal ions, inactivating the ions that cannot normally react with other elements or ions to produce precipitates or scale results in metal buffering and solubilization (Weber and Werner, 2007). Therefore, extra chelating agents could increase Fe 2þ solubility to enhance sulfate radical formation.…”

Synthesis and Reactivity of an Aminocarbene Osmium Complex Formed by Double C–H Activation of a NCH3 Unit

“…[4] Although the relevant NMR spectroscopic data of 4 [δ(CHR) = 11.38 ppm; δ(CHR) = 231. [4] These two complexes contain a linear P-Os-P unit.…”

“…These complexes were prepared from the osmium(IV) precursor [OsH 2 Cl 2 (PiPr 3 ) 2 ] and the functionalized phosphane by reductive elimination of H 2 and ligand exchange. [4] The seemingly more simple approach to obtain, for example, [ [5] led to a surprising result: instead of the expected product the Fischer-type oxocarbene-osmium(II) complex cis,cis-[OsCl 2 {κ 2 (C,P)-CHOCH 2 CH 2 PiPr 2 }{κ 2 -(P,O)-iPr 2 PCH 2 CH 2 OMe}] was obtained. [6] In this paper we report that the phosphaneamine iPr 2 PCH 2 CH 2 NMe 2 behaves similar to the phosphane ether iPr 2 PCH 2 CH 2 OMe and affords upon treatment with 3 ] an aminocarbene-osmium(II) derivative.…”