Aspects of the coordination chemistry of rac-trans-1,2-diphosphinocyclohexane and the preparation of reinforced 9aneP3 and 9anePN2 macrocyclesCCDC 1015695-1015699. For crystallographic data in CIF or other electronic format see 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 ]BF 4 and [Ag( t -chxnP 2 ) 2 ]BF 4 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 1 R ,2 R - and 1 R ,2 S -diaminocyclohexane (chxn) have been coordinated to Mn( i ) and Fe( ii ) templates and similarly employed for the formation of new 1,4-diamino-7-phosphamacrocycle (9anePN 2 ) complexes. Rac , trans -1,2-diphosphinocyclohexane ( t -chxnP 2 ) has been prepared and coordinated to Cu( i ), Ag( i ), Fe( ii ) and Mn( i ) and the latter two metals used as templates for the formation of structurally reinforced 9aneP 3 and 9anePN 2 macrocycles.