Metal-to-Ligand π-Bonding in Some Nickel(II) Pseudo-Halide Complexes with Heterocyclic Aromatic Amines

Nelson, S. M.; Shepherd, T. M.

doi:10.1021/ic50028a009

Cited by 57 publications

(14 citation statements)

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“…The Dq values of the selenocyanate complexes are higher than that of the corresponding thiocyanate complexes which reveals that the ligand field strength of the former is higher than that of the latter (16)(17)(18). The metalligand bond in selenocyanates is more covalent than in thiocyanates as is evidenced by the values of B'.…”

Section: Ii) the Difference In Total Softness Values [(Ate'(m-hg)]mentioning

confidence: 89%

Structural studies on di-µ-thiocyanato(N,S)-bis(ligand)diisothiocyanato metal(II)bis(triphenylphosphine)mercury(II) and selenocyanate analogs

Singh¹,

Yadav²

1979

Can. J. Chem.

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P. P. SIYGH and S. P. YADAV. Can. J . Chem. 57.394(1979) (PPh,) Introduction Pyridine or its derivatives reacts with MHg(XCN), (M = Co(II), Ni(II), Cu(II), Zn(I1); X = S, Se), to yield polymeric bridged complexes (1-4) of the type ) ( X C N ) , (~~) , M ( N C X ) , H <~~ which the ligand is coordinated to M. On account of this, the maximum coordination of M is achieved, but the coordination number of Hg(I1) remains four against the maximum of six. This paves the way to further coordination at this site. It is at this site the triphenylphosphine has been introduced and an entirely new series of mixed-ligand complexes synthesized and studied. Binuclear mixed-metal mixed-ligand monomeric bridged con~plexes o f the type (XCN),-(L),M(I\JCX),Hg Second Method (L),M(NCX), was first prepared by stirring the solution o f M(NCX), in methanol with the excess o f the solution o f the ligand (py or nia) in the same solvent for 6 h . T o the suspension o f Hg(XCN), in methanol, a solution o f PPh, in the same solvent was added in 1 : 2 molar ratio and stirred for 10 h to get (Ph,P)2Hg(XCN),. In each reaction a solid mass was separated which was filtered, washed with the solvent, and dried in cacuo. (L),M(NCX), waa dissolved in a mixture o f methanol and pyridine or nicotinamide. This solution was added to the suspension o f (Ph3P)2Hg(XCN)2 in methanol in Results and DiscussionOn account of the insolubility of these complexes crystals. The structure of the complexes, therefore, have been proposed on the basis of analytical data, of >(XCN),(L),M(NCX)~H~<.

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Section: Ii) the Difference In Total Softness Values [(Ate'(m-hg)]mentioning

confidence: 89%

Structural studies on di-µ-thiocyanato(N,S)-bis(ligand)diisothiocyanato metal(II)bis(triphenylphosphine)mercury(II) and selenocyanate analogs

Singh¹,

Yadav²

1979

Can. J. Chem.

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“…For related literature, see: Goher et al (2002); Liu et al (2006); Nelson & Shepherd (1965); Schreiner & Hamm (1973).…”

Section: Related Literaturementioning

confidence: 99%

“…Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT and SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL. Azido-Ni II compounds with mono-N donored pyridine based co-ligands have been investigated early with respect to their metal-to-ligand π-bonding features (Nelson & Shepherd, 1965), magnetic circular dichroism and crystal field (Schreiner & Hamm, 1973). Recently, the crystal structures of two relative compounds, {[Ni(4-ethylpyridine) 4 (N 3 )].…”

Section: Data Collectionmentioning

confidence: 99%

catena-Poly[[bis(pyridine-κN)nickel(II)]-di-μ-azido-κ⁴N¹:N³-[bis(pyridine-κN)nickel(II)]-di-μ-azido-κ⁴N¹:N¹]

Song

Ming-Jian

et al. 2007

Acta Cryst E

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In the structure of the title compound, [Ni2(N3)4(C5H5N)4]n, neutral chains of NiII atoms are bridged alternately by double end‐on and double end‐to‐end azide bridges. Each NiII center is located on a crystallographic general position and in a slightly distorted octahedral coordination environment with two pyridine ligands in the trans positions. Both end‐on and end‐to‐end double azide bridges become equivalent because of the inversion centers lying between each pair of adjacent NiII atoms. In the chain, the Ni...Ni separations across the end‐on and end‐to‐end azide bridges are 3.236 (4) and 4.975 (4) Å, respectively, and the end‐on azide bridging Ni—N—Ni angle is 100.8 (2)°.

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“…The coordination between pyridine derivatives and nietal ions i~lvolves both U-bonding and =-bonding contributions (20)(21)(22)(23), which produce opposite effects on the C=N band intensity; viz. U-bonding lon:ers the C=N band intensity, whereas =-bonding enhances the C : N hand intensity.…”

Section: Infrared Intensitiesmentioning

confidence: 99%

“…Since the usual linear relation of free energy (6) is valid for the system being studied13 it follons that \\;here y is a constant characteristic of the functioilal group, the attacking electrophile, and the reaction medium. Co~nbination of [23], [21], and [19] gives…”

Section: Correlation Betzueen the Infrared Intensities And The Coordimentioning

confidence: 99%

STUDIES OF METAL COMPLEXES OF PYRIDINE DERIVATIVES: THE EFFECTS OF COORDINATION UPON INFRARED INTENSITY OF THE FUNCTIONAL GROUP IN Β-Cyanopyridine

Brewer¹,

Wong²

1966

Can. J. Chem.

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'The infrared intensity of the C=S group in P-cyanopyridine co~nplexes with some first-row transition metal ions (Zn(II), Cu(II), Ni(II), Co(1 I), Fe(II), and Mn(I1)) in aqueous solution has been measured. The coordination between the nitrogen atom on the pyridine ring and these metal ions exerts a marked change in the magnitude of the band intensity of the functional group. This can be interpreted in terms of a simple molecular orbital model and the relative magnitudes of o-bonding arid T-bonding involved in the con~plexes. A "coordination constant" is introduced for this system, and a linear correlation between these constants and the C S V band intensities of the metal complexes is obtained from both the experimental data and theoretical considerations.The intensities of the infrared absorption band associated with the C=N functionaI group vibration in aliphatic and aromatic cyanides have been studied to a considerable extent (1-5). In particular, studies of the C=N band infrared intensities in a number of substituted benzonitriles showed that substituents on the ring exerted a pronounced effect on the magnitude of the functional group intensity; electron-reIeasing substituents enhanced the functional group intensity, whereas electron-attracting substituents loxvered the intensity.The correlation of the intensity variations in substituted benzonitriles with the socalled "substitution constants" (6) has also been studied. The results suggest that there is an essentially linear relation between the logarithm of the intensity and the substitution constant for both nleta-and para-substituted conlpounds in various solvents.In the present investigation, the intensities of the C=N band in heterocyclic cl-anides were studied. 0-Cyanopyridine was chosen as a starting point for these studies. An attempt has been made to determine the effects of coordination bet\\reen the nitrogen atoll1 on the pyridine ring and some first-row transition illeta1 ions on the C=N band intensity. A sinlple molecular orbital model is presented; this model is used to give a quantitative treatnlent of the data for the system, for \vhich purpose a "coordination constant" is introduced. EXPERIMENTAL illaterials 0-Cyanopyridine, supplied by the L. Light and Co. Ltd., was recrystallized three times from etherpetroleum ether (60-68") mixture.Pyridine, reagent grade supplied by British Drug Houses (Canada) Ltd., was dried over potash overnight and then redistilled twice.3-Pyridinol, supplied by Aldrich Chemical Co. Inc., \\.as recrystallized twice in absolute alcohol and then purified by sublimation.Most of the transition metal salts were nitrates supplied by the G. Frederick Slnith Chem. Co., and were recrystallized from water several times.Deuterium oxide was obtained from hIerck Sharp and Dohme of Canada Ltd., and had a n assay of 9'J.7y0 ' 0 2 0 .Carbonate-free potassium hydroxide solution for the p H titration was prepared by the method of Schvvarzenbacll (7).Canadian Journal of Cl~elnistry. J'oluine 44 (19fjG) 1407 Can. J. Chem. D...

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Metal-to-Ligand π-Bonding in Some Nickel(II) Pseudo-Halide Complexes with Heterocyclic Aromatic Amines

Cited by 57 publications

References 1 publication

Structural studies on di-µ-thiocyanato(N,S)-bis(ligand)diisothiocyanato metal(II)bis(triphenylphosphine)mercury(II) and selenocyanate analogs

Structural studies on di-µ-thiocyanato(N,S)-bis(ligand)diisothiocyanato metal(II)bis(triphenylphosphine)mercury(II) and selenocyanate analogs

catena-Poly[[bis(pyridine-κN)nickel(II)]-di-μ-azido-κ⁴N¹:N³-[bis(pyridine-κN)nickel(II)]-di-μ-azido-κ⁴N¹:N¹]

STUDIES OF METAL COMPLEXES OF PYRIDINE DERIVATIVES: THE EFFECTS OF COORDINATION UPON INFRARED INTENSITY OF THE FUNCTIONAL GROUP IN Β-Cyanopyridine

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Metal-to-Ligand π-Bonding in Some Nickel(II) Pseudo-Halide Complexes with Heterocyclic Aromatic Amines

Cited by 57 publications

References 1 publication

Structural studies on di-µ-thiocyanato(N,S)-bis(ligand)diisothiocyanato metal(II)bis(triphenylphosphine)mercury(II) and selenocyanate analogs

Structural studies on di-µ-thiocyanato(N,S)-bis(ligand)diisothiocyanato metal(II)bis(triphenylphosphine)mercury(II) and selenocyanate analogs

catena-Poly[[bis(pyridine-κN)nickel(II)]-di-μ-azido-κ4N1:N3-[bis(pyridine-κN)nickel(II)]-di-μ-azido-κ4N1:N1]

STUDIES OF METAL COMPLEXES OF PYRIDINE DERIVATIVES: THE EFFECTS OF COORDINATION UPON INFRARED INTENSITY OF THE FUNCTIONAL GROUP IN Β-Cyanopyridine

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catena-Poly[[bis(pyridine-κN)nickel(II)]-di-μ-azido-κ⁴N¹:N³-[bis(pyridine-κN)nickel(II)]-di-μ-azido-κ⁴N¹:N¹]