Aspects of the coordination chemistry of rac-trans-1,2-diphosphinocyclohexane and the preparation of reinforced 9aneP(3) and 9anePN(2) macrocycles

作者：Edwards Peter G^*; Kariuki Benson M; Newman Paul D; Tallis Huw A; Williams Craig

来源：Dalton Transactions, 2014, 43(41): 15532-15545.

DOI：10.1039/c4dt02239d

Racemic trans-1,2-diphosphinocyclohexane (t-chxnP(2)) has been synthesised and its coordination chemistry to Cu(I), Ag(I), Mn(I) and Fe(II) investigated. Compounds of empirical formula [Cu(t-chxnP(2))(2)]BF4 and [Ag(t-chxnP(2))(2)]BF4 have been prepared as isomeric mixtures and the solid-state structure of both complexes determined by single-crystal techniques. The Cu(I) complex is a monomeric species which crystallises with one ligand bearing the R,R configuration and the other being the S,S isomer whereas the Ag(I) complex crystallises as a polymer containing both chelating and bridging t-chxnP(2) ligands with 3- and 4-coordinate Ag(I) centres and argentophilic bonds. The bidentate diprimary phosphine has been coordinated to Mn(I) and Fe(II) templates and used as a P-2 unit for the formation of chiral (albeit racemic) 1,4,7-triphosphamacrocycles (9aneP(3)). In addition 1R,2R- and 1R,2S-diaminocyclohexane (chxn) have been coordinated to Mn(I) and Fe(II) templates and similarly employed for the formation of new 1,4diamino-7-phosphamacrocycle (9anePN(2)) complexes.

• 出版日期2014