trans-Cyano(6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine)cobalt(III) bis(perchlorate) hydrate andtrans-hydroxo(6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine)cobalt(III) bis(perchlorate)

Abstract

trans-Cyano(6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine)-cobalt(III) bis(perchlorate) hydrate and trans-hydroxo(6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine)-cobalt(III) bis(perchlorate)

Tuning the metal-to-metal charge transfer energy of cyano-bridged dinuclear complexes

“…8,20 The Fe-C coordinate bonds around the ferrocyanide moiety are as expected, 23 2,3 In fact the trans-I N-based diastereomeric form has been seen in all but one structurally characterised, pentadentate-coordinated Co III complex of L 14 . 21,22 The coordinate bonds around the Ru atom are the same within experimental error and consistent with those found in other hexacyanoruthenate(II) containing structures. [24][25][26] A notable feature is the pronounced distortion of the C1a-N1a-Co angle (162.8(8)°) from its ideally linear value.…”

“…The pentadentate macrocycles L 14 and L 14S have been identified in a variety of geometric (trans/cis) and N-based diastereomeric forms when complexed with Co III . 2,8,[18][19][20][21][22] However, both trans-[L 14S CoNCFe(CN) 5 ] − and trans-[L 14 CoNCRu(CN) 5 ] − exhibit NMR spectra consistent with mirror plane symmetry, which can only be present when the macrocycles adopt a conformation where the pendent amine is trans to the bridging cyano ligand. Interestingly, trans-[L 14S CoNCFe(CN) 5 ] − forms exclusively from cis-[CoL 14S Cl] 2+ (or an unpurified isomeric mixture of cis-and trans-[CoL 14S Cl] 2+ ).…”

Immobilisation of electroactive macrocyclic complexes within titania films

“…This has been seen in other related pendent amino-macrocyclic cyanocobalt(III) complexes of L 1 and L 2 . 7,26, 42 The hydroxyl proton attached to O2 was located from difference maps and the disparity in the C21-O1 and C21-O2 bond lengths supports this assignment. The secondary amine N-donors adopt the trans-I (RSRS) configuration where all H-atoms lie on the same side of the macrocycle.…”

“…The Co-N bond lengths (Table 1) are typical of pentadentate coordinated Co III complexes of L 1 and L 2 and their derivatives. 3,7,26,38,41, 42 The cyano ligand exhibits a significant trans influence on the Co-N5 bond length, which is notably longer than the other four Co-N bonds. This has been seen in other related pendent amino-macrocyclic cyanocobalt(III) complexes of L 1 and L 2 .…”

“…The six-coordinate geometry of the complex is completed by a C-bound cyano ligand trans to the pendent amine. The Co-N bond lengths ( 42 The cyano ligand exhibits a significant trans influence on the Co-N5 bond length, which is notably longer than the other four Co-N bonds. This has been seen in other related pendent amino-macrocyclic cyanocobalt(III) complexes of L 1 and L 2 .…”