A Rare μ-Hydroxo-Bridged Species. Synthesis, Structure, and Properties of μ-Hydroxo(tetraphenylporphyrinatomanganese(III))(phthalocyaninato(azido)chromium(III)), [(TPP)Mn−O(H)−CrPc(N₃)]

Abstract

A novel ditetrapyrrolic, heteroleptic, and heterometallic (Mn-Cr) mu-hydroxo-bridged complex has been prepared, and its structural and general properties have been studied. The species mu-hydroxo(tetraphenylporphyrinatomanganese(III))(phthalocyaninato(azido)chromium(III)), [(TPP)Mn-O(H)-CrPc(N3)], isolated as a chloronaphthalene (ClNP) solvate, has been structurally characterized by single-crystal X-ray work. The two (TPP)Mn and CrPc(N3) fragments are held together by the bridging mu-hydroxo ion with long Mn-O [1.993(5) A] and Cr-O [1.976(5) A] bond distances and a Mn-O(H)-Cr angle of 163.7(3) degrees . The five-coordinate Mn center in the (TPP)Mn fragment is displaced from the TPP rigorously planar central N4 core by 0.128 A, and the environment is typical of a Mn(III) high-spin site. The six-coordinate Cr(III) in the CrPc(N3) moiety lies practically in the plane of the phthalocyanine macrocycle (displacement toward the azido group: 0.054 A). The average Mn-N(pyr) and Cr-N(pyr) bond distances are 2.011(6) and 1.982(6) A, respectively, and the Mn-Cr bond distance is 3.929(2) A. The porphyrin and phthalocyanine rings are in an almost eclipsed position [5.16(2) degrees ], and the mean planes of the two macrocycles form a dihedral angle of 5.79(4) degrees. Crystal data for [(TPP)Mn-O(H)-CrPc(N3)].2ClNP, C76H45CrMnN15O.2C10H7Cl: a = 16.645(3) A, b = 17.692(4) A, c = 25.828(5) A, alpha = 90 degrees , beta = 98.79(3) degrees , gamma = 90 degrees , space group P2(1)/c (No. 14), V = 7517(3) A(3), Z = 4, R1 = 0.086, and wR2 = 0.267. IR and UV-vis-near-IR spectral and room temperature magnetic susceptibility data of the [Mn-Cr] species are also presented.

Can Cyclen Bind Alkali Metal Azides? A DFT Study as a Precursor to Synthesis

“…The N 3 ‐side‐on structures M‐2 a (M=Li, Na, Rb) and M‐2 b (M=K, Cs) are similar to some crystal structures of transition metal azide‐NNNN containing macrocycles –,,. The N 3 unit of these structures adopts a side‐on conformation similar to that in the transition‐metal tetraaza analogues.…”

“…The N 3 unit of these structures adopts a side‐on conformation similar to that in the transition‐metal tetraaza analogues. However, the M−N−N bond angle is larger in these transition‐metal azides with M−N−N bond angles ranging from 121.3(2) ° to 149.7(8) ° for M=Co, Fe, Cu, Cr, Mn and Ru,–,, compared with 101.6–85.6 ° (BP86; B3LYP, 104.2–86.9 °) for the alkali metal N 3 ‐side‐on structures investigated in this work (Supporting Information, Tables S3 and S4). Several transition‐metal azide crystal structures– have the cyclam unit (1,4,8,11‐tetraazacyclotetradecane) as the macrocycle, which has four N−H groups as potential coordinating groups.…”

“…The ECPs not only model the core electrons and treat the valence electrons in an explicit manner, but they also take into consideration scalar relativistic effects, which are important in high atomic number elements . The reliability of the BP86 functional with the 6‐311G(d,p) and the Stuttgart RSC 1997 ECP basis sets in molecules of the type studied in this work has been established in recent studies involving metal azide‐macrocyclic complexes ,. The DFT calculations were repeated using the Becke three parameter non‐local hybrid exchange correlation functional, B3LYP .…”

Construction of a supramolecule comprising [2,3,9,10,16,17,23,24-octakis(2,6-dimethylphenoxy)phthalocyaninato]zinc(II) and (5,10,15,20-tetraphenylporphyrinato)zinc(II)

“…A structure survey using CSD web interface (Groom et al, 2016) returned one entry of a phthalocyanine-TPP complex (CCDC entry 621715), and six compounds similar to the Pc moiety of the title compound that were further divided into two groups (CCDC entries 946716, 946717, 946718 and 279644, 761420, 76142, respectively). The phthalocyanine-TPP complex of CCDC 621715 is a (Mn-Cr) -hydroxidobridged complex (Donzello et al, 2006). Conversely, compounds in the first group, which are similar to Pc, differ from Pc only in the types of metal ions (Pr III , Nd III and Sm III ; Li et al, 2014).…”

Dedication to Professor Claudio Ercolani on the Occasion of his 75th Birthday

“…[15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] 3) Dioxygen activation, oxygen atom transfer, and oxidative catalysis. [28][29][30][31] 4) Synthesis and investigation of the molecular and electronic structure of single-atom bridged homo-and heterobimetallic µ-oxodiiron(III) bisphthalocyaninates; [32][33][34][35][36][37][38][39][40][41][42][43] as well as µ-nitrido [44][45][46][47][48][49][50][51] and µ-carbido [52][53] complexes of general formula (L)M-X-M'(L') (X = O, N, C; L and L' phthalocyanine or porphyrin dianions) containing iron in high-valence states (Fe IV ).…”