Products from the Reaction ofmeso-Tetrakis(4-halophenyl)porphinato-manganese(II) and Hexacyanobutadiene (HCBD): Formation of π-[HCBD]22− Dimers,μ-[HCBD].−, σ-[HCBD].−, and [C4(CN)5O]−

Abstract

The reaction of hexacyanobutadiene (HCBD) and meso-tetrakis(4-chlorophenyl)porphinatomanganese(II) pyridine [MnIITClPPpy] (1Cl) leads to two phases of [MnIIITClPPpy][HCBD].PhMe (alpha-2Clpy, beta-2Clpy). Similarly, the reaction of HCBD and tetrakis(4-bromophenyl)porphinatomanganese(II) pyridine [MnIITBrPPpy] (1Br) leads to two products [MnIIITBrPPpy] [HCBD] * PhMe (2 Brpy) and [MnIIITBrPP][HCBD]*2 PhMe (3Br). The structure of dark-green alpha-2Clpy consists of one porphyrin unit with MnIII in a square pyramidal coordination environment axially bound to one pyridine. The cation forms [MnIIITCIPPpy](2)2+ as cofacial dimerized porphyrins. Each [HCBD]*- is nonplanar with a torsion angle of 170.8(4) degrees about the center C-C bound, and forms [HCBD](2)2- dimers in the solid state with sub-van der Waals contacts of 3.325 and 3.340 angstroms. The magnetic data above 10 K obey the Curie-Weiss expression with a theta of -2.5 K, and mueff (300 K) = 4.91 muB as expected for S=2MnIII and S = 0 [HCBD](2)2-. The magnetic data for alpha-2Clpy can be fit with an zero-field-splitting D of -1.45 K. beta-2 Clpy consists of one porphyrin unit with MnIII in a distorted octahedral coordination environment axially bound to py and to a monodentate [HCBD]*- bound via an exo-nitrile. [HCBD]*- is nonplanar with a torsion angle of 169.7(5) degrees about the center C-C bound. The ueff (350 K) is 5.09 muB; however, the magnetic data do not obey the Curie-Weiss expression above 70 K. The low temperature data may be fit with a theta of -5.4 K. The data was modeled to an isolated S = 2 and S = 1/2 dinuclear spin system with J/kappaB = - 90 K. Decomposition of [HCBD]*- to [C4(CN)5O]- was evidenced by the determination of the structure of [MnIIITCIPP][C4(CN)5O] 2PhMe (3ClO). Crystals of 3 Cl-O were prepared by reaction of HCBD and 1Cl in the presence of a drop of water. The molecular structure consists of [HCBD]*-trans-mu-N-2,3-bound to [MnIIITBrPP]+ forming a 1-D coordination polymer of alternating [MnIIITBrPP]+ and [HCBD]*-. The intrachain Mn***Mn distance was 10.675(3) angstroms, with important interchain Mn***Mn distances of 10.832, 11.016, and 14.696 A. The magnetic data were fit to a Curie-Weiss law (10 < T< 290 K) with a theta of -3.5 K, and D = 0.3 K with mueff = 4.97 muB at 300 K.

Synthesis, FT–IR characterization and crystal structure of aqua(5,10,15,20-tetraphenylporphyrinato-κ4N)manganese(III) trifluoromethanesulfonate

“…The average equatorial manganese-N(pyrrole) distance is 1.998 (9) Å , which is close to related [Mn III (Porph)(X)] + ion complexes (Porph and X are a porphyrinato and a monodentate neutral ligand, respectively), e.g. [Mn III (TClPP)(py)] + (TClPP is 5,10,15,20-(tetra-4-chlorophenyl)porphyrinato) where the average Mn-N(pyrrole) bond length is 2.007 (2) Å (Rittenberg et al, 2000). In Fig.…”

One‐Dimensional, Cofacial Porphyrin Polymers Formed by Self‐Assembly of meso‐Tetrakis(ERE Donor) Zinc(II) Porphyrins

“…Several combinations have been investigated, including those of ruthenium(II) porphyrins with diphosphine ligands,26 phosphorus(V) porphyrins with oxygen ligands,27, 28 and manganese(III) porphyrins with 4,4′‐bipyridyl ligands 29. Polymers formed from polycyanoalkenes and manganese(II)30–32 or iron(III) porphyrins33 were prepared by Miller and co‐workers. Porphyrin coordination polymers consisting of A–B‐type monomers (thus forming [⋅⋅A–B⋅⋅] ∞ polymers or cyclic oligomers) have also been studied thoroughly.…”

“…Keywords: chlorophylls · coordination modes · porphyrins · selfassembly · zinc manganese(II) [30][31][32] or ironA C H T U N G T R E N N U N G (III) porphyrins [33] were prepared by Miller and co-workers. Porphyrin coordination polymers consisting of A-B-type monomers (thus forming [··A-B··] 1 polymers or cyclic oligomers) have also been studied thoroughly.…”

Structure and magnetic ordering of a 2-D MnII(TCNE)I(OH2) (TCNE = tetracyanoethylene) organic-based magnet (Tc = 171 K)

“…The source of the water is adventitious, as has been previously observed. 12 Guided by this discovery, the same material was directly synthesized via the reaction of TCNE, MnI 2 (THF) 3 , and water in CH 2 Cl 2 . 13 Mn(TCNE)I(OH 2 ) contains an octahedral Mn II bonded to four m 4 -[TCNE] À with 2.20(2) and 2.25(1) A ˚Mn-N bond distances [average Mn-N = 2.22(2) A ˚], central C-C and C-CN distances of 1.37(2) and 1.409(8) A ˚, respectively, that are characteristic of [TCNE] À .…”