Reactions of aminophosphines and aminobis(phosphines) with aldehydes and ketones: Coordination complexes of the resultant aminobis(alkylphosphineoxides) with cobalt, uranium, thorium and gadolinium salts - Crystal and molecular structures of Ph2P(O)C

摘要

The reaction of aminophosphines and aminobis(phosphines) with aldehydes leads to either insertion of carbon fragments into the P(III)-N bonds or formation of alpha-hydroxyphosphine oxides through P(III)-N bond cleavage. Reaction of 1,2-C6H4{N(H)PPh2}(2) with paraformaldehyde gives the P(III)-N bond inserted product 1,2-C6H4{N(H)CH2P(O)Ph-2}(2), whereas 1,3-C6H4{N(H)PPh2}(2) forms an analogous product but with an additional methylene group inserted between the two nitrogen centers through nucleophilic addition to form a bicyclic derivative, 1,3-C6H4{Ph2P(O)CH2N(mu-CH2)NCH2P(O)Ph-2}. Reactions of Ph2PN(H)Ph with aromatic aldehydes, RCHO (R = C6H4OH-o, 5-BrC6H3OH-o, (eta(5)-C5H5)Fe(eta(5)-C5H4-)) lead to the insertion of 'RCH' into the P(III)-N bond to give Ph2P(O)CH(R)N(H)Ph. The reactions of aminobis(phosphine), Ph2PN(Bu-n)PPh2 with both aromatic and aliphatic aldehydes lead to the formation of ot-hydroxy phosphine oxide derivatives of the type Ph2P(O)CH(R)OH, through P(111)-N bond cleavage. The N-bridged bis(phosphine oxide) (PrN)-Pr-n(CH2V(O)Ph-2)(2) readily forms chelate complexes with U(VI), Th(IV) and Gd(III) derivatives. (c) 2005 Elsevier Ltd. All rights reserved.