Coordination Compounds of Nickel(II) Salts with Substituted Pyridines. Square-Planar, Tetrahedral, and Octahedral Compounds of 3,4- and 3,5-Dimethylpyridine

Buffagni, S.; Vallarino, L. M.; Quagliano, J. V.

doi:10.1021/ic50015a015

Cited by 73 publications

(8 citation statements)

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“…For example, tetraalkyltin compounds and boron halides react readily to give alkylboron dihalides or dialkylboron halides. 7 The possibility that this type of exchange reaction might also occur between tetraalkyltin compounds and fluorophosphoranes was first suggested to us by the above boron system. If successful this reaction would provide a rather useful synthetic route to alkylfluorophosphoranes.…”

Section: Discussionmentioning

confidence: 97%

The Reaction of Phosphorus Pentafluoride and Tetraalkyltin Compounds

Treichel¹,

Goodrich²

1965

Inorg. Chem.

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Alkyltetrafluorophosphoranes can be prepared in good yield by the room temperature reaction of phosphorus pentafluoride and tetraalkyltin compounds. Careful investigation of the stoichiometry of this reaction indicates that this reaction is not as straightforward as one might expect, however. In all of the reactions attempted some of the phosphorus was retained in the nonvolatile residue of the reaction. Evidence is presented which indicates that this residue contains a complex of the formula R3SnPF6, whose structure is probably similar to other known compounds RsSnX (X = CIO,•, BF4, AsFe, and SbF6).Alkyltetrafluorophosphoranes have been synthesized by a number of different methods. The method de-Contribution from the

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Section: Discussionmentioning

confidence: 97%

The Reaction of Phosphorus Pentafluoride and Tetraalkyltin Compounds

Treichel¹,

Goodrich²

1965

Inorg. Chem.

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“…The packing of one structure type is disrupted, so to speak, by the shift of a methyl group; the process of readjustment to a new stable crystal structure includes a change in the coordination to the other structure type. It is known (Buffagni, Vallarino & Quagliano, 1964) that the blue compound Ni(3,5-dimethylpyridine)4-(C104)2 dissociates in dichloromethane solution to give free perchlorate ions and the diamagnetic and presumably square-planar cation Ni(3,5-dimethylpyridine) 2+. The solution is yellow and nearly identical in its electronic spectrum with a solution of the 3,4-dimethylpyridine complex compound.…”

Section: Discussionmentioning

confidence: 99%

Crystal structures of complexes of nickel perchlorate with substituted pyridines. II. Tetrakis-(3,4-dimethylpyridine)nickel(II) perchlorate

Madaule-Aubry¹,

Busing²,

Brown³

1968

Acta Crystallogr Sect B

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X-ray structure analysis shows that the yellow solid Ni(3,4-dimethylpyridine)4(C104)2 contains the complex ion Ni(3,4-dimethylpyridine) 2+ in which nickel exhibits square-planar coordination, in agreement with the interpretation of spectroscopic and magnetic studies [Buffagni, Vallarino & Quagliano, bwrg. Chem. (1964), 3, 671]. Crystals of the compound have the Laue symmetry 4/m; a = b = 10"3277 (14), e= 15.6136 (37)/~, Z= 2. Intensities of 1028 independent reflections (Cu Ka radiation, sin 0/2 <0.639) were recorded with the Oak Ridge computer-controlled diffractometer and were corrected for absorption. All of the carbon and nitrogen atoms of the organic ligand except the carbon of the 3-methyl group were immediately recognizable directly as Ni-N and Ni-C peaks in a Patterson map. Coordinates for the other atoms, which were not found from the Patterson map because of disorder in the structure, were obtained from a Fourier synthesis. The Patterson map showed that the symmetry of the disordered crystal structure is either very nearly or exactly that of space group 14/m, which was assumed to be the appropriate one in the subsequent analysis. After full-matrix least-squares refinement, the final value of the usual discrepancy index R(F) is 0.071. The organic ligands are in twofold rotational disorder about their axes from nitrogen to 4-methyl. The symmetry of the disordered ion is, in the statistical sense, that of point group 4/m. The planes of the ligands are perpendicular to the mirror m. The bonds Ni-N, which are rotated 19-9 ° from coincidence with the directions of the vectors a and b, are 1.897 (3)/~ long. Two of the oxygen atoms of the perchlorate ion are held on the fourfold axis 0,0,z by non-bonded contacts with other atoms, and their parameters are fairly well determined. The other two oxygen atoms and the chlorine atom are in fourfold disorder about the axis 0,0,z, and their parameters are poorly determined.

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“…(b) Yellow diamagnetic compounds: py=3,4-dimethylpyridine (Buffagni et al, 1964), 4-methylpyridine (Moore et al, 1964), 4-aminopyridine (Moore et al, 1964).…”

Section: Introductionmentioning

confidence: 99%

“…One interesting series of compounds whose magnetic and spectral properties have been studied is the series Ni(py)4(CIO4)2, where py stands for pyridine and various substituted pyridines. The compounds studied fall into two classes: Drago, 1965), 3,5-dimethylpyridine (Moore, Gayhart & Bull, 1964;Buffagni, Vallarino & Quagliano, 1964), 3-bromopyridine (Moore et al, 1964), 4-isopropylpyridine (Moore et al, 1964).…”

Section: Introductionmentioning

confidence: 99%

Crystal structures of complexes of nickel perchlorate with substituted pyridines. I. Bisperchloratotetrakis-(3,5-dimethylpyridine)nickel(II)

Madaule-Aubry¹,

Brown²

1968

Acta Crystallogr Sect B

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X-ray structure analysis shows that the blue solid Ni(3,5-dimethylpyridine)4(CIO4)2 is an octahedral complex compound in which the perchlorate ions are coordinated to the nickel ion, in agreement with the interpretation of spectroscopic and magnetic studies (Moore, Gayhart, & Bull, J. hwrg. and Nuclear Chem. (1964), 26, 896; Buffagni, Vailarino & Quagliano, lnorg. Chem. (1964), 3, 671). Crystals of the compound have the space-group symmetry 141/acd; a=b=15.8759 (17), c=26.7581 (25),~, Z=8. Intensities of 1712 independent reflections (Cu K~ radiation, sin 0/2<_0.639) were recorded with the Oak Ridge computer-controlled diffractometer and were corrected for absorption. The structure was solved essentially from Patterson and Fourier syntheses as a heavy-atom problem. Disorder in the arrangement of the perchlorate group made the location of the three perchlorate oxygen atoms not coordinated to nickel rather difficult; these atoms were located eventually by use of the method of least-squares, the occupancy factors of closely spaced possible positions being adjusted to find the actual positions. Although the parameters of the remainder of the structure are fairly precisely determined, those of most of the atcms of the perchlorate group are not well determined because of the disorder; and the final value of the usual discrepancy index R(F) has the rather high value 0.101. The nickel atom of the asymmetric unit is located at the point 0, k, ~ of the Wyckoff set (b) (point-group symmetry 222); the perchlorate group is in a disordered arrangement about the twofold axis x, k + x,-~, which is perpendicular to the average plane of the nickel and nitrogen atoms defined by the twofold axes x, ¼-x,~ and 0,¼,z. The angle between the Ni-O bond and the twofold axis is 9.2:'; the Ni-O bond length is 2-187 (4) °. The four organic ligands are in a propeller-like arrangement (pitch ~47 ~) around the axis through the perchlorate. The Ni-N bond length is 2.093 (2)/~. The nitrogen atoms are alternately 0-065 A above and 0.065 ,~ below their average plane. The structure is very similar to that of Ni(pyridine)4C12, which has the same space-group symmetry and nearly the same translations a and b (Porai-Koshits, Structure Reports (1954), 18, 749).

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Coordination Compounds of Nickel(II) Salts with Substituted Pyridines. Square-Planar, Tetrahedral, and Octahedral Compounds of 3,4- and 3,5-Dimethylpyridine

Cited by 73 publications

References 3 publications

The Reaction of Phosphorus Pentafluoride and Tetraalkyltin Compounds

The Reaction of Phosphorus Pentafluoride and Tetraalkyltin Compounds

Crystal structures of complexes of nickel perchlorate with substituted pyridines. II. Tetrakis-(3,4-dimethylpyridine)nickel(II) perchlorate

Crystal structures of complexes of nickel perchlorate with substituted pyridines. I. Bisperchloratotetrakis-(3,5-dimethylpyridine)nickel(II)

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