Coordination chemistry of H‐spirophosphorane ligands towards pentacarbonylchlororhenium(I) – synthesis, structure and catalytic activity of complexes

Abstract

Synthesis of a group of carbonyl rhenium coordination compounds with hydrospirophosphorane ligands was carried out and described. Different symmetrical HP(OCH2CH2NH)2L1, HP(OCH2CMe2NH)2L2, HP(OC6H4NH)2L3, and unsymmetrical ligands HP (OCMe2CMe2O)(OC6H4NH) L4 were found to coordinate to the rhenium center as bidentate P,N donor ligands yielding fac‐[ReCl (CO)3Ln], where n = 1–4. Furthermore, monodentate coordination was also observed in some cases, as was clearly presented in the case of [ReCl(CO)2(L4‐κ2P,N)(L4‐κP)] complex. All of the complexes were characterized using optical spectroscopy. Single‐crystalX‐ray diffraction was also performed in the case of fac‐[ReCl(CO)3L3], fac‐[ReCl(CO)3L4], [Re(CO)2(L2)2]Cl and [ReCl (CO)2(L4‐κ2P,N)(L4‐κP)] samples. Complexes [ReCl(CO)3L3] and [ReCl (CO)3L4], both bearing rings of conjugated double bonds within hydrospirophosphorane ligands, exhibited luminescence. Catalytic properties of rhenium complexes were assessed using the representative fac‐[ReCl (CO)3L2] complex in the dimerization reaction of terminal alkynes. An efficient and selective procedure for synthesis of the E‐enynes was developed. Coupling of (2‐chlorophenyl)acetylene was mediated by [ReCl (CO)3L2]/TBAF system with a 100% conversion rate. Different substituents within aromatic alkynes were tolerated and the resulting products were dependent on the nature of the substituents.

Investigation of Hydrophosphorylation Reaction of Pentacoordinate Hydrospirophosphorane and Electron‐Deficient Alkenes Catalyzed by Organic Phosphine

“…Organophosphorus compounds occupy an important place in many materials sciences and biologically active substances for medical and agricultural use, such as agrochemicals, pharmaceuticals and natural products [1–3] . Moreover, they are widely employed as versatile chemical reagents or as ligands for transition metal in organic synthesis [4–9] . Among the various synthetic approaches to organophosphorus compounds, the direct construction of phosphorus‐carbon (P−C) bond is of particular importance.…”

“…Hydrospirophosphorane (HSP) is an important kind of the pentacoordinated phosphorus compounds containing a P−H bond, which may be used as a hydrophosphorylation reagent. In recent years, HSPs are also found to be a new type of potential ligand to catalyze organic reactions [8] . Furthermore, our group found that pentacoordinate spirophosphorane was a type of potential organocatalyst to catalyze organic reactions [25] .…”

“…[1][2][3] Moreover, they are widely employed as versatile chemical reagents or as ligands for transition metal in organic synthesis. [4][5][6][7][8][9] Among the various synthetic approaches to organophosphorus compounds, the direct construction of phosphorus-carbon (PÀ C) bond is of particular importance. The addition of hydrogen phosphine to an unsaturated carbon À carbon bond is one of the most important reactions.…”

“…In recent years, HSPs are also found to be a new type of potential ligand to catalyze organic reactions. [8] Furthermore, our group found that pentacoordinate spirophosphorane was a type of potential organocatalyst to catalyze organic reactions. [25] The addition reactions of olefins and tricoordinate or tetracoordinate phosphorus compounds bearing PÀ H bond have been reported.…”

The two faces of platinum hydrospirophosphorane complexes—Not only relevant catalysts but cytotoxic compounds as well

“…[ 9 ] While low‐valent rhenium(I) complex [ReCl(CO) 3 {P(OCH 2 CMe 2 NH)OCH 2 CMe 2 NH 2 }] was successfully utilized in dimerization reaction of substituted enynes. [ 10 ] Moreover, we have previously reported on rhodium(I) hydrospirophosphorane effective catalysts for the isomerisation of 1‐hexene. In the presence of modified ligand P (OPh) 3 , rhodium complexes have been shown to catalyze regioselectively hydroformylation of 1‐hexene.…”