Insertion of Carbon Fragments into P(III)−N Bonds in Aminophosphines and Aminobis(phosphines): Synthesis, Reactivity, and Coordination Chemistry of Resulting Phosphine Oxide Derivatives. Crystal and Molecular Structures of (Ph<sub>2</sub>P(O)CH<sub>2</sub>)<sub>2</sub>NR (R = Me, <i><sup>n</sup></i><sup></sup>Pr, <i><sup>n</sup></i><sup></sup>Bu), Ph<sub>2</sub>P(O)CH(OH)<i><sup>n</sup></i><sup></sup>Pr, and <i>cis</i>-[MoO<sub>2</sub>Cl<sub>2</sub>{(Ph<sub>2</sub>P(O)CH<sub>2</sub>)<sub>2</sub>NEt-κ<i>O</i>,κ<i>O</i>}]
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Reactions of N-aryl and N-alicyclic derivatives of aminophosphines with paraformaldehyde lead to methylene insertion into P−N bond followed by oxidation of phosphorus from the P(III) to P(V) state. When N-alkyl derivatives are reacted with paraformaldehyde, dimerization takes place to afford bis(phosphine oxide)s of the type Ph2P(O)CH2N(R)CH2P(O)Ph2 (R = Me, nPr, nBu). Aminobis(phosphines) also undergo methylene insertion when treated with paraformaldehyde to give bis(phosphine oxides) Ph2P(O)CH2N(R)CH2P(O)Ph2 (R = Me, Et, nPr, iPr, nBu) in good yield. The reaction of aminophosphines with aromatic aldehydes ArCHO leads to insertion of “ArCH” into the P−N bond to give Ph2P(O)CH(R)N(H)Ph (R = C6H5, furfuryl, o-C6H4OH), but with aliphatic aldehydes such as butanal, P−N bond cleavage takes place to afford α-hydroxy phosphine oxide. The reaction of aminobis(phosphines) with both aromatic and aliphatic aldehydes leads to the formation of α-hydroxy phosphine oxides through P−N bond cleavage whereas the reaction with furfural leads to the P−N bond insertion. The structure of the α-hydroxy derivative Ph2P(O)CR(H)(OH)nPr shows intermolecular hydrogen bonding between OH and PO oxygen. The phosphine oxide derivatives act as bidentate ligands and form chelate complexes with Co(II), Mo(VI), Th(IV), and U(VI) derivatives. The crystal structure of the molybdenum complex, cis-[MoO2Cl2{(OPPh2CH2)2NEt-κO,κO}], shows the distorted octahedral geometry around Mo with two oxo groups cis to each other.
