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• W1588630270 abstract "Reduction of the imine functions of 7RS,14SR-(5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)nickel(II) gives the meso–meso (5RS,7RS,12SR,14SR) and rac-meso (5RS,7RS,12RS,14SR) isomers of (5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradecane)nickel(II), [Ni(mmL2)]2+ and [Ni(rmL2)]2+, in approximately 6:1 proportions. Most compounds of [Ni(mmL2)]2+ have the amine in planar coordination with the 1RS,4RS,8SR,11SR N-configuration III (labelled β) of the nitrogen centres as square-planar singlet ground state salts β-[Ni(mmL2)]X2 (X−=ClO4 −, 1/2[ZnCl4]2−) or as octahedral triplet ground state compounds trans-β-[Ni(mmL2)X2] (X−=Cl−, Br−, I−, N3 − NO3 −, HCO3 −, MeCO3 −, NCS−, NO2 −, CN−), trans-β-Ni(mmL2)(CN)(ClO4), bis-adducts trans-β-[Ni(mmL2)Y2](ClO4)2 (Y=MeCN, DMSO, DMF, pyridine, MeNO2, NH3) and trans-μ-anion polymeric compounds β-[Ni(mmL2)Z] (Z2−=C2O4 2−, SO4 2−, CO3 2−, [Ni(CN)4]2−). Centrosymmetrical trans-β-[Ni(mmL2)(NO2-N)2] has N-configuration III, with all chelate rings in optimum chair or gauche conformations, with all substituents equatorially oriented and with mean distances NiNamine=2.083(2), NiNnitro=2.183(2) Å. Reaction of trans-β-[Ni(mmL2)(HCO3)2]·H2O with alcohols form compounds of mono-alkyl carbonate esters, trans-β-[Ni(mmL2)(CO2OR)2]. Compounds cis-α-[Ni(mmL2)(A)]ClO4 (A=pentane-2,4-dionato−, 1/2C2O4 2−) have the macrocycle folded. The acac− compound has the 1RS,4RS,8RS,11RS N-configuration V with mean distances NiN=2.121(3), NiO=2.042(3) Å and angles N(4)NiN(11)=173.2(1), N(1)NiN(8)=95.1(1)°, with one six-membered chelate ring in a chair conformation with the substituents equatorially oriented and the other in a boat conformation that orients the substituents pseudo-equatorially. The folded macrocycle compounds react with acid to form a metastable [Ni(mmL2)]2+ cation, isolated as the perchlorate salt δ-[Ni(mmL2)](ClO4)2 with the 1RS,4RS,5SR,7SR,8SR,11RS,12RS,14RS configuration, N-configuration II. The square-planar cation is tetrahedrally twisted with N-atoms ±0.103 Å and Ni atom 0.043 Å from the best N4 plane, with mean NiN=1.933(6) Å. One six-membered chelate ring is in a chair conformation with the substituents equatorially oriented, and the other in a twist conformation with the methyl substituent axially and the phenyl substituent equatorially oriented. Relative strain energies for the isomeric cations were calculated by molecular mechanics." @default.
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• W1588630270 date "2003-11-01" @default.
• W1588630270 modified "2023-09-24" @default.
• W1588630270 title "Compounds of nickel(II) with 5RS,7RS,12SR,14SR-5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradecane, mmL2; the structures of δ-[Ni(mmL2)](ClO4)2, trans-β-[Ni(mmL2)(NO2-N)2] and cis-α-[Ni(mmL2)(acac)]ClO4" @default.
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• W1588630270 doi "https://doi.org/10.1016/s0020-1693(03)00226-3" @default.
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