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

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

Developing the Kharasch Reaction in Aqueous Media: Dinuclear Group 8 and 9 Catalysts Containing the Bridging Cage Ligand Tris(1,2‐dimethylhydrazino)diphosphane

“…The Ru(1)-P(1) bond length of 2.3173(10) Å compares well with those previously reported for the related cage-like aminophosphane complexes [RuCl 2 (η 6 -p-cymene)(PTA)] [Ru-P 2.296(2) Å] [17] and [RuCl 2 (η 6 -p-cymene)(THPA)] [Ru-P 2.294(2) Å]. [7] It is also interesting to note that, when compared to the X-ray structure of the free ligand, [10] the coordination of THDP to ruthenium does not alter significantly its geometry, the intra-ligand bond lengths (Ϯ0.05 Å) and angles (Ϯ10°) remaining almost unchanged. (14),…”

“…[5] In this context, we have recently reported that the structurally related trihydrazinophosphaadamantane ligand (THPA; see Figure 1) [6] is also a suitable ligand for the solubilization of transition-metal catalysts in water. [7] In particular, several water-soluble Ru II , Rh I , and Ir I THPA complexes could be prepared and successfully applied to the catalytic isomerization of allylic alcohols into carbonyl compounds, as well as in the cycloisomerization of (Z)-enynols into furans, in aqueous media. [7] Figure 1.…”

“…[7] In particular, several water-soluble Ru II , Rh I , and Ir I THPA complexes could be prepared and successfully applied to the catalytic isomerization of allylic alcohols into carbonyl compounds, as well as in the cycloisomerization of (Z)-enynols into furans, in aqueous media. [7] Figure 1. Structure of the cage-like ligands PTA, THPA, and THDP.…”

Exploring Rhodium(I) Complexes [RhCl(COD)(PR3)] (COD = 1,5-Cyclooctadiene) as Catalysts for Nitrile Hydration Reactions in Water: The Aminophosphines Make the Difference

“…However, the introduction of heteroatoms in β-position with respect to the C≡N unit resulted beneficial and the hydration processes proceeded in these cases to completion. Thus, chloroacetonitrile (4t), trichloroacetonitrile (4u), phenoxyacetonitrile (4v) and methoxyacetonitrile (4w) were converted to the corresponding primary amides 5r-s in ≥ 95% GC-yield after 1-24 h of reaction (entries [20][21][22][23]. 43 This may be again understood in terms of the enhancement of the electrophilicity of the nitrile carbon atom by the substituents.…”

Efficient Phosphorus Catalysts for the Halogen‐Exchange (Halex) Reaction

“…Addition of n-Buli (2 equivalents) in hexane to a suspension of 1 in THF followed by treatment with Br 2 and addition of 1,2-dihydrophosphole (2) [17] , 1,3,5-triaza-7-phosphaadamantane (3) (PTA) [18] , triphenylphosphine (4), and 4,6,9-trimethyl-1,3,4,6,7,9-hexaaza-5-phosphatricyclo[3.3.1.1 3,7 ] decane (5) (THPA) [19,20] led respectively to the corresponding (PNP) + salts 8a-11a. The structures were assigned on the basis of NMR data as well as X-ray diffraction studies for the salt 9a.…”