The dual role of cis-[RuCl2(dmso)4] in the synthesis of new water-soluble Ru(II)–phosphane complexes and in the catalysis of redox isomerization of allylic alcohols in aqueous–organic biphasic systems

Abstract

New air-stable, water-soluble Ru(II)-phosphane complexes were synthesized in high purity by the reaction of cis-[RuCl2(dmso)4] with 2 equivalents of 1,3,5-triaza-7-phosphaadamantane (pta) and its N-methyl and N-benzyl derivatives (pta-Me and pta-Bn, respectively). All new complexes were characterized by elementary analysis and spectroscopic methods (NMR, ESI  1 and the new complexes actively catalyzed the isomerization of allylic alcohols. MS) and the molecular structures of cis-cis-trans-[RuCl2(dmso)2(pta)2], cis-cis-trans-

Neutral 1,3,5‐Triaza‐7‐phosphaadamantane‐Ruthenium(II) Complexes as Precursors for the Preparation of Highly Water‐Soluble Derivatives

“…The spectroscopic characterization of 12 (Figure S21) as well as its X‐ray structure (Figure ) are in good agreement with previous reports ,…”

“…An ideal precursor might have one or more PTA coligands for solubility and one or more dmso ligands (with appropriate geometry) for facile replacement by the linker. We confirmed and expanded the results originally reported by Kathó and co-workers on this topic [11] and investigated the unexplored reactivity of the Ru II complex cis,cis,trans-RuCl 2 (dmso-S) 2 (PTA) 2 (12) towards bpy and bpyAc and obtained cis,cis-Ru(bpy)Cl 2 (PTA) 2 (16) and cis,cis-Ru(bpyAc)Cl 2 (PTA) 2 (17, as a 50:50 mixture of the two stereoisomers 17a and 17b).…”

“…[8,[12][13][14][15][16][17] prepared and characterized. We also found that PTA reacts rapidly with cis,fac-RuCl 2 (dmso-O)(dmso-S) 3 (11) and trans-RuCl 2 (dmso-S) 4 (13) under mild conditions through the replacement of pairs of mutually trans dmso ligands with high selectivity, even when in stoichiometric defect. Thus, 11 affords cis,cis,trans-RuCl 2 (dmso-S) 2 (PTA) 2 (12), whereas 13 gives 1.…”

“…It has moderate steric demand (cone angle 103°), good σand π-bonding abilities [comparable to those of P(OMe) 3 ] and, above all, it typically imparts excellent water solubility to its complexes. By virtue of their solubility, PTA-metal complexes have been investigated as homogeneous catalysts, either directly in aqueous solution or under aqueous-organic biphasic conditions, [3][4][5][6][7][8][9][10][11] and as potential anticancer drugs. [8,[12][13][14][15][16][17] prepared and characterized.…”

“…In addition, we also investigated the reactivity of the wellknown Ru II Cl(dmso) complexes cis,fac-RuCl 2 (dmso-O)(dmso-S) 3 (11) and trans-RuCl 2 (dmso-S) 4 (13) towards PTA. An ideal precursor might have one or more PTA coligands for solubility and one or more dmso ligands (with appropriate geometry) for facile replacement by the linker.…”