Etude De La Reactivite De Quelques Phosphor(iii)adamantanes

Water‐Soluble Group 8 and 9 Transition Metal Complexes Containing a Trihydrazinophosphaadamantane Ligand: Catalytic Applications in Isomerization of Allylic Alcohols and Cycloisomerization of (Z)‐Enynols in Aqueous Medium

“…Synthesis of THPA and its Water-Soluble Complexes As commented above, the trihydrazinophosphaadamantane ligand THPA (2) can be easily obtained by desulfuration of the thiophosphane 4,6,9-trimethyl-5-thio-1,3,4,6,7,9-hexaaza-5-phosphatricyclo[3.3.1.1 3,7 ]-decane (1), which is readily accessible in a multigramscale through the reaction of S=PCl 3 with methylhydrazine and further treatment with formaldehyde. Nevertheless, in our original preparation of 2 the desulfuration process required the use of a large excess of tri-n-butylphosphane, which acts both as reducing agent and solvent, as well as an extremely long reaction time (15 days), making the synthesis rather tedious.…”

“…[6] Surprisingly, despite its great potential, the coordination chemistry of this water-soluble ligand has been completely neglected, [Fe(CO) 4 A C H T U N G T R E N N U N G (THPA)] being the only transition-metal complex reported till now in the literature. [7] With all these precedents in mind and stimulated by the increasing demand for novel, efficient watersoluble catalysts, we decided to explore the coordination chemistry and the catalytic applications of the THPA ligand, starting from an optimized synthesis of THPA as well as the preparation of the first ruthenium, rhodium and iridium complexes containing this P donor ligand. They have proved to be soluble in organic solvents and in water, and have been successfully used to promote the catalytic isomerization of allylic alcohols into carbonyl compounds in both THF and aqueous media.…”

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Abstract: An optimized synthesis of the 2,4,10-trimethyl-1,2,4,5,7,10-hexaaza-3-phosphatricyclo-[3.3.1.1 3,7 ]decane ligand (THPA) is described. It

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“…{arene = C 6 H 6 (5a), p-cymene (5b); THPA-Me = 1,2,4,10-tetramethyl-2,4,5,7,10-pentaaza-1-azonia-3-phosphatricyclo-[3.3.1.1 3,7 ]decane}. The arene-ruthenium(II) complexes 4a-d and 5a and b are efficient catalysts for the redox isomerization of allylic alcohols into carbonyl compounds in both THF and aqueous media.…”

Water soluble diphosphine ligands based on 1,3,5-triaza-7-phosphaadamantane (PTA-PR2): Synthesis, coordination chemistry, and ruthenium catalyzed nitrile hydration

“…[31,32] A variety of lower-rim (C 3 N 3 ring) modified derivatives have been published involving opening of the cage, [21,22,23,25,27,33] expansion of the ring, [34,35] substitution of a methylene with SO 2 , [24,36] or trisubstitution of the triazacyclohexane ring. [19] Upper-rim derivatives of PTA have been synthesized by addition of aldehydes, ketones, imines, and carbon dioxide to lithiated PTA (PTA-Li) resulting in the formation of carboxylates, [20] β-phosphino alcohols, [20,28,30] or β-amino phosphines; [10] Scheme 1.…”