12,13,25,26-Tetraaza-2,15-dithia[3.3]phenanthrolinophane. Synthesis, conformational study and complexation reactions

A new class of mixed aza–thioether crown containing a 1,10-phenanthroline sub-unit

“…The Ni-N bond lengths are similar to those found in other nickel@) complexes of phen derivative^. '^ The three Ni-S lengths [2.4286(7b 2.4440 (7) A] are slightly longer than those normally observed in complexes of aliphatic thia-and mixed thia-aza-crown ethers ' v 2 such as mi ([18]aneN2S4)]2+ ( [18]aneN2S4 = 1,lOdithia-4,7,13, 16-tetraazacyclohexadecane)2 mi-S 2.403(6)-2.416 (7) A] and are indicative of uncompressed Ni-S bonds (cJ: the sum of the ionic radii of Ni2+ and S2-, 2.44 A). to be 11 655 cm-'; this value is intermediate between that of mi( [18]aneN6)]2+ and [Ni([l 8]aneS,)I2+ ( [18]ane-N, and -s6 = 1,4,7,10,13,16-hexaaza-and 1,4,7,10,13,16-hexathiacyclooctadecane) (1 1 200 and 12 290 cm-' respectively) and between that of mi(phen),12+ and [Ni(NCMe),12+ (12 400 and 10 650 cm-1).20 It is comparable with those of other thiaaza crown ether complexes of Nil' and interestingly higher than those observed for BiL(NCMe),12 + { 10 290-1 1 090 cm-'; L = [12]aneS4 (1,4,7,10-tetrathiacyclododecane), [ 14]aneS4 (1,4,8,11 -tetrathiacyclotetradecane) or [ 1 6]aneS4 (1,5,9,13tetrathiacyclohexadecane) for x = 2 and [15]aneS, (1,4,7,10, 13-pentathiacyclopentadecane) for x = l}.2' The magnetic susceptibility obeys the Curie law from 4 to 300 K with peff = 3.09 pB.…”

“…Bond lengths and angles for the complex are summarised in Table 1. The nickel (11) ion is bound to the pentadentate macrocycle via two N-donors of the phen unit, Ni-N 2.025(2) and 2.01 3(2) A, and three thioether S-donors of the thioether linker, Ni-S 2.4340(8), 2.4440(7) (trans to phen) and 2.4286 (7) A (trans to NCMe). The octahedral co-ordination sphere is completed by an MeCN molecule, Ni-N 2.070(2) A.…”

Conformationally locked mixed aza–thioether macrocycles: synthesis and structures of complexes of PdII, PtII and RhIII of 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane

“…The 13 C NMR chemical shifts for the complexes [ML] 2ϩ (M = Pd or Pt) and [RhL(Cl)] 2ϩ in CD 3 CN solution are reported in Table 3 and are compared with those for the free macrocycle 16 (the crystal structure numbering scheme has been adopted for their assignment). Only six peaks for the aromatic region and three for the thioether one are observed in 13 C NMR spectra; this suggests that the three complexes exist in solution in only one form having a C s symmetry with a plane of reflection passing through the metal and the S(3) atoms and bisecting the N(1)᎐M᎐N(2) angle. With respect to the free macrocycle, the carbon atoms next to S(1) and S(2) are deshielded whereas those next to S(3) are shielded for the complexes of Pd II and Pt II ; the situation is different for Rh III in which all the carbon atoms are deshielded.…”

“…With respect to the free macrocycle, the carbon atoms next to S(1) and S(2) are deshielded whereas those next to S(3) are shielded for the complexes of Pd II and Pt II ; the situation is different for Rh III in which all the carbon atoms are deshielded. The 13 C NMR chemical shifts do not change upon cooling to 238 K. Furthermore, the 13 C NMR spectra recorded in the solid state on the three complexes Table 1 Selected interatomic distances (Å), angles and torsions (Њ) for…”

“…[3][4][5][6][7][8][9][10][11] The presence of rigid heterocyclic molecules such as pyridine, 2,2Ј-bipyridine (bipy) and 1,10-phenanthroline (phen), which carry hard N-donor atoms, as part of a macrocycle ligand has been shown to stabilize low-valent metal complexes as well as to have a marked influence on the coordination geometry at the metal centre. 12, 13 Interest in complexes of substituted derivatives of bipy and phen is based mainly on their catalytic, redox and photoredox properties, 14 as well as on their use as building blocks for supramolecular devices. 15 We have recently reported the synthesis and coordinating properties of new mixed aza-thioether crowns incorporating the 1,10-phenanthroline sub-unit with Ni II .…”