Cyclohexylbis(hydroxymethyl)phosphane: A Hydrophilic Phosphane Capable of Forming Novel Hydrogen‐Bonding Networks

Abstract

The cyclohexyl‐substituted (hydroxymethyl)phosphane CyP(CH2OH)2 (1) has been prepared by reaction of the corresponding primary phosphane CyPH2 with aqueous formaldehyde. Compound 1 has been used as building block for the synthesis of new functionalized water‐soluble phosphorus compounds. Thus, Mannich‐type condensation of 1 with excess glycine affords the air‐stable amino acid phosphane conjugate CyP[CH2N(H)CH2COOH]2 (2). Simple oxidation of 1 with hydrogen peroxide and elemental sulfur leads to the crystalline chalcogenide derivatives CyP(O)(CH2OH)2 (3) and CyP(S)(CH2OH)2 (4). X‐ray diffraction analyses of the latter revealed distinct intermolecular hydrogen bonding motifs and possess different types of hydrogen bond networks to each other due to the different proton acceptor ability of the chalcogen atom X of the P=X group (X = O, S): while the oxygen atom of the P=O moiety in 3 serves as proton acceptor, affording a P=O–HO bifurcated network, the sulfur atom of the P=S group denies hydrogen bonding interactions. In addition, the ligand ability of 1 has been studied towards Pt(+2) and Cu(+1) ions: Reaction of 1 with Pt(COD)Cl2 (COD = cycloocta‐1,5‐diene) furnishes the air‐stable complex cis‐[PtCl2{CyP(CH2OH)2}2] (5), while the crystalline dimeric Cu(+1) complex [CuI{CyP(CH2OH)2}2]2 (6) results from the reaction of CuI with two molar equivalents of 1. The complex 6 shows a intermolecular hydrogen bonding pattern different from that of 1, 3 and 4, respectively. The new coordination compounds 5 and 6 represent metal‐phosphane labelled alcohols which are promising building blocks for the synthesis of metal‐based drugs. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Biologically inspired phosphino platinum complexes

“…Gilbertson and coworkers [26][27][28], as well as others [29], have demonstrated this with the incorporation of a series of non-natural amino acids into larger peptides. This and similar work [30] have established the ability of catalysts built with peptides to initiate and stabilize structure with enzyme like hydrogen bonding networks. The ligands and metal complexes reported here provide another route, specifically through the peptide backbone, rather than the amino acid side chains, to incorporate large peptides into homogeneous catalysts to investigate the role of the outer-coordination sphere.…”

The Primary Phosphine Renaissance

“…For our purposes we chose to study the reaction of (R)-5 with formaldehyde ( Fig. 1.12); phosphines with the resulting substituents have found numerous applications in catalysis and medicinal chemistry [3,13,14,[68][69][70][71][72][73][74][75].…”

Cyclooctene epoxidation with H2O2 and single crystal X-ray determined crystal structures of new molybdenum and tungsten catalysts bearing the hydrophilic ligand hydroxymethyldiphenylphosphine oxide

“…These type of ligands can be described as functionalized hydrophilic phosphines, for which related derivatives have been studied during the past decades [13]. They are expected to be good ligands for organometallic catalysts since they combine the bonding attributes of phosphine oxide ligands with the increased solubility in polar solvents of hydrophilic alcohols [14].…”