(Pentamethylcyclopentadienyl)iridium‐PTA (PTA = 1,3,5‐Triaza‐7‐phosphaadamantane) Complexes and Their Application in Catalytic Water Phase Carbon Dioxide Hydrogenation

Abstract

The water-soluble iridium(III) complexes [Cp*Ir(PTA)Cl 2 ] (1) and [Cp*Ir(PTA) 2 Cl]Cl (2) (PTA = 1,3,5-triaza-7-phosphaadamantane) have been synthesised and characterised by spectroscopy and X-ray crystallography. The complexes were evaluated as catalyst precursors for the hydrogenation of CO 2 and hydrogen carbonate in aqueous solutions, in the absence of amines or other additives, under relatively mild con-

Unusual Metal-Coordinated Zwitterionic P−C−N−C−N−C Phosphido Adducts

“…7 As part of continuing studies in our group investigating supramolecular interactions in (di)tertiary phosphines, 8 we recently reported easily accessible intramolecular H-bonded phosphine analogues of the cage ligand PTA (PTA = 1,3,5-triaza-7-phosphaadamantane). 8a The recent surge in interest with PTA, and its analogues, can be traced to the ease of chemical modification 9 and diverse coordination, cytotoxic and catalytic properties. 10 Herein we report the structural characterization of two peculiar homodinuclear zwitterionic Pd II and Pt II complexes of a partially delocalized sixmembered P{cyclo-CH 2 N(R)CHN(R)CH 2 } (R = 4-FC 6 H 4 CH 2 , C 6 H 5 CH 2 ) bridging phosphido ligand.…”

Reactions of N-heterocyclic ligands with substitutionally labile organometallic complexes, [(η5-C5R5)Fe(CO)2E]BF4

“…These data are given in the Experimental Section. Both the 1 H and 13 C NMR spectra did not show any evidence of decomposition. Peaks remained sharp even after allowing the solution to stand for 10 h. Furthermore, the mass spectroscopy data of compounds 3a and 4b collected in 100% water confirmed the stability of these compounds in water.…”

“…This is clearly reflected in the single crystal X-ray diffraction data presented in Table 3. 13 Tables 3 and 4, respectively. Crystals of compound 7 were obtained as yellow plates that crystallized in the monoclinic P2 1 /c space group, with three independent molecular cations and anions each in the asymmetric unit, while compound 8 crystallized in the orthorhombic Pna21 space group as yellow prisms, with one cation and a counterion in the asymmetric unit.…”

“…Calc. for C 13 A Schlenk tube was charged with a solution of complex 1 (1.921 g, 5.68 mmol) in CH 2 Cl 2 (15 ml) and a solution of DABCO (0.212 g, 1.89 mmol) in CH 2 Cl 2 (10 ml) added. The mixture was stirred for 6 h at room temperature after which an orange precipitate formed.…”

“…Some of these complexes have found application in aqueous phase and biphasic catalytic systems [9][10][11][12][13] as well as in pharmaceuticals [5,7]. The synthesis of water-soluble organometallic derivatives has been widely achieved by the design of water-soluble ligands that, when incorporated into the coordination sphere of the metal, impart water-solubility to the complexes.…”