The Configuration of Tervalent Nitrogen. A Bicyclic Hydrazine Derivative<sup>1</sup>

Buhle, E. Loren; Moore, A. M.; Wiselogle, F. Y.

doi:10.1021/ja01241a009

Cited by 60 publications

(12 citation statements)

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“…[29,30] Other commercially available chemical reagents and solvents were of analytical grade and were purified by standard procedures prior to use. Ϫ FT-IR spectra were recorded on a Nicolet 170SX spectrometer at room temperature.…”

Section: Methodsmentioning

confidence: 99%

Novel Diazamesocyclic Ligands Functionalized with Pyridyl Donor Group(s) − Synthesis, Crystal Structures, and Properties of Their Copper(II) Complexes

Shang

et al. 2001

Eur. J. Inorg. Chem.

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Two novel diazamesocyclic ligands based on l,5-diazacyclooctane (DACO) and functionalized with additional pyridyl donor groups, namely 1,5-bis(2-pyridylmethyl)-1,5-diazacyclooctane (L 1 ) and 1-(2-pyridylmethyl)-1,5-diazacyclooctane (L 2 ), have been synthesized and characterized, as have their Cu II complexes. Crystal structure analyses revealed that with Cu(ClO 4 ) 2 L 1 forms a five-coordinate mononuclear complex [Cu II L 1 Cl]ClO 4 (1), whereas L 2 forms a µ-Cl − -bridged dinuclear complex [Cu II (L 2 )Cl] 2 (ClO 4 ) 2 (2). Furthermore, it has been found that the apical chloride anion of 1 may be easily exchanged by azide anion, forming the mononuclear complex [Cu II L 1 (N 3 )]ClO 4 (3). There is a notable difference between 3 and 1 in that 3 forms a quasi-two-dimensional network through intermolecular C−H···O hydrogen bonds and π−π stacking interactions. Each Cu II center in the three com-

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Section: Methodsmentioning

confidence: 99%

Novel Diazamesocyclic Ligands Functionalized with Pyridyl Donor Group(s) − Synthesis, Crystal Structures, and Properties of Their Copper(II) Complexes

Shang

et al. 2001

Eur. J. Inorg. Chem.

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“…The ligand 1,5-bis(1-methyl-1H-imidazol-2-ylmethyl)-1,5-diazacyclooctane dihydrochloride was prepared by the reaction of 1,5-diazacyclooctane hydrobromide and 1-methyl-2-chloromethylimidazole hydrochloride in ethanol solution in the presence of KOH (Buhle et al, 1943;Billman & Dorman, 1962) and the details will be published elsewhere. A mixture of Co(ClO 4 ) 2 Á6H 2 O (370 mg, 1 mmol) and 1,5bis(1-methyl-1H-imidazol-2-ylmethyl)-1,5-diazacyclooctane hydrochloride (340 mg, 1 mmol) was dissolved in methanol (30 ml, room temperature).…”

Section: Methodsmentioning

confidence: 99%

[1,5-Bis(1-methyl-1H-imidazol-2-ylmethyl-κN³)-1,5-diazacyclooctane-N,N′]chlorocobalt(II) perchlorate

Shang

et al. 2000

Acta Crystallogr C

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The crystal structure of the title compound, H 26 N 6 )]ClO 4 , consists of discrete [CoCl(C 16 H 26 N 6 )] + cations and perchlorate anions. The ®ve-coordinate Co II atom has four nitrogen donors from the new mesocyclic ligand 1,5bis(1-methyl-1H-imidazol-2-ylmethyl)-1,5-diazacyclooctane [CoÐN 2.046 (3)±2.214 (4) A Ê ], and a chloride anion at the apical site [CoÐCl 2.3184 (13) A Ê ]. The coordination geometry of the complex is essentially square pyramidal. The mesocyclic ligand takes a boat±chair con®guration and the two imidazole pendants are not coplanar. The dihedral angle between the two imidazole planes is 15.97 . An H atom from the 1,5diazacyclooctane group effectively blocks the axial coordination site opposite the Cl ligand.Comment 1,5-Diazacyclooctane (DACO) derivatives bearing two additional functional donor pendants can strongly coordinate to transitional metal centers, forming square-pyramidal ®vecoordinate or square-planar four-coordinate complexes (Grapperhaus & Darensbourg, 1998;Nielson et al., 1971;Bu et al., 1999).The four donor atoms of such tetradentate ligands coordinate to the central metal ions nearly in a plane and the DACO backbone usually adopts a boat±chair con®guration. This con®guration will force a portion of the chelate framework across to the axial coordination position, and will sterically restrict further axial coordination to the metal center. Therefore, such DACO derivatives can be used as very good ligands for the construction of metal complexes with a squareplanar or square-pyramidal con®guration. The interesting chemistry of such DACO derivatives prompted us to create more such ligands by modifying DACO with heterocyclic donor pendants to obtain new complexes with functional properties. We synthesized a new mesocyclic ligand functionalized by two imidazole donor pendants, 1,5-bis(1-methyl-1H-imidazol-2-ylmethyl)-1,5-diazacyclooctane and its cobalt(II) complex, [CoCl(C 16 H 26 N 6 )]ClO 4 , (I). We report herein the crystal structure of this new complex.The structure of (I) comprises discrete [CoCl(C 16 H 26 N 6 )] + cations and perchlorate anions (Fig. 1). In the complex cation, the Co II atom is ®ve coordinate. 1,5-Bis(1-methyl-1H-imidazol-2-ylmethyl)-1,5-diazacyclooctane acts as a tetradentate ligand through one pair of nitrogen donors of the mesocyclic ring and the two N atoms of the imidazole pendants. The coordination geometry about the Co II atom can be described as square pyramidal. The four nitrogen donors of the ligand coordinate to the central Co II in one plane, with a chloride anion occupying an apical position. The ( value used to describe the degree of trigonal distortion is 0.006 (Addison et al., 1984), i.e. nearly zero, indicating that the distortion is very small. The Co atom is above the mean plane formed by atoms N1, N2, N3 and N5 by 0.549 A Ê towards the apical Cl ligand. The two imidazole pendants are not coplanar, their planes forming an angle of 15.97 .The six-membered CoNCH 2 CH 2 CH 2 N rings in H 26 N 6 )]ClO 4 adopt boat±chair con®gurations. ...

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“…The ligand 1,5-diazacyclooctane (DACO) dihydrobromide was prepared according to a literature method (Buhle et al, 1943;Billman & Dorman, 1962). A mixture of Ni(Ac) 2 Á4H 2 O (373 mg, 1.5 mmol) and DACO dihydrobromide (822 mg, 3 mmol) was dissolved in methanol (30 ml) at room temperature.…”

Section: Methodsmentioning

confidence: 99%

Bis(1,5-diazacyclooctane-N,N′)nickel(II) dibromide

Leng

et al. 2000

Acta Crystallogr C

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The crystal structure of the title complex, [Ni(C(6)H(14)N(2))(2)]Br(2), consists of discrete [Ni(C(6)H(14)N(2))(2)](2+) cations and bromide counter-anions. The Ni(II) ion is at the center of symmetry and is four-coordinated by four nitrogen donors of the mesocyclic ligand 1,5-diazacyclooctane (DACO) [Ni-N 1.935 (2)-1.937 (2) A]. The coordination geometry of Ni(II) can be considered as square planar and both DACO ligands take the boat-chair conformation. The bromide anions are hydrogen bonded with the nitrogen donors of the ligands to form a macrocycle-like ring system.

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The Configuration of Tervalent Nitrogen. A Bicyclic Hydrazine Derivative¹

Cited by 60 publications

References 0 publications

Novel Diazamesocyclic Ligands Functionalized with Pyridyl Donor Group(s) − Synthesis, Crystal Structures, and Properties of Their Copper(II) Complexes

Novel Diazamesocyclic Ligands Functionalized with Pyridyl Donor Group(s) − Synthesis, Crystal Structures, and Properties of Their Copper(II) Complexes

[1,5-Bis(1-methyl-1H-imidazol-2-ylmethyl-κN³)-1,5-diazacyclooctane-N,N′]chlorocobalt(II) perchlorate

Bis(1,5-diazacyclooctane-N,N′)nickel(II) dibromide

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The Configuration of Tervalent Nitrogen. A Bicyclic Hydrazine Derivative1

Cited by 60 publications

References 0 publications

Novel Diazamesocyclic Ligands Functionalized with Pyridyl Donor Group(s) − Synthesis, Crystal Structures, and Properties of Their Copper(II) Complexes

Novel Diazamesocyclic Ligands Functionalized with Pyridyl Donor Group(s) − Synthesis, Crystal Structures, and Properties of Their Copper(II) Complexes

[1,5-Bis(1-methyl-1H-imidazol-2-ylmethyl-κN3)-1,5-diazacyclooctane-N,N′]chlorocobalt(II) perchlorate

Bis(1,5-diazacyclooctane-N,N′)nickel(II) dibromide

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The Configuration of Tervalent Nitrogen. A Bicyclic Hydrazine Derivative¹

[1,5-Bis(1-methyl-1H-imidazol-2-ylmethyl-κN³)-1,5-diazacyclooctane-N,N′]chlorocobalt(II) perchlorate