Structural characterization of a novel platinum(IV) complex produced by deprotonation of coordinated amino groups of the rigid ligand cis,cis-1,3,5-triaminocyclohexane

Sarneski, Joseph E.; McPhail, Andrew T.; Onan, Kay D.; Erickson, Luther E.; Reilley, Charles N.

doi:10.1021/ja00464a058

Cited by 52 publications

(28 citation statements)

References 2 publications

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“…From the difference maps two hydrogen atoms were found to be bound to the ligand atom O(1), which has an effect on the Pt-O(1) bond length. This bond length is 2.039(4) Å, which is in good agreement with Pt(IV)-O (aqua) bond distances reported previously [27][28][29]. The Pt-O(2) bond distance is shorter at 1.978(4) Å, which is typical for axial Pt(IV)-hydroxido bond lengths.…”

Section: Description Of Crystal Structuressupporting

confidence: 89%

“…Jeffrey has listed O ··· O distances in hydrogen bonds in some organic anions, obtained by neutron diffraction [24]. Typical values range from 2.393(3) Å for imidazolium hydrogenmaleate [25] [27][28][29] and these all have bond lengths of about 2.04 Å, which would indicate that this bond does not take on the full characteristics of a Pt(IV)-aqua bond. The short hydrogen bond may account for this anomaly and cause the oxygen to retain more of a hydroxido characteristic with the hydrogen atom shared equally.…”

Section: Description Of Crystal Structuresmentioning

confidence: 99%

See 1 more Smart Citation

Structural and anticancer properties of hydrogen bonded diphenyl phosphate adducts of Pt(IV) complexes: The importance of pKa matching

Failes

Battle

Chen

et al. 2012

Journal of Inorganic Biochemistry

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Section: Description Of Crystal Structuressupporting

confidence: 89%

Section: Description Of Crystal Structuresmentioning

confidence: 99%

Structural and anticancer properties of hydrogen bonded diphenyl phosphate adducts of Pt(IV) complexes: The importance of pKa matching

Failes

Battle

Chen

et al. 2012

Journal of Inorganic Biochemistry

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“…On the contrary, reaction of [Pt II (bipy)Cl 2 ] with tach gave rise to [Pt IV (bipy)(H À2 tach)(OH 2 )] 2 , rather than a square planar [Pt II (bipy-k 2 N,N')(tach-k 2 N,N')] 2 . [9] This result clearly illustrates the difficulties in the bidentate coordination of tach. For taci and tmca, which carry additional substituents in the 2-, 4-, and 6-positions, even further destabilization of such a bidentate coordination mode is to be expected.…”

Section: Structural Properties Of Dapi Complexesmentioning

confidence: 85%

The Coordination Chemistry ofcis-3,5-Diaminopiperidine and Substituted Derivatives

et al. 2000

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An efficient and convenient method for the preparation of cis-3,5-diaminopiperidine (dapi) has been established and the coordination chemistry of this ligand with CoII, CoIII, NiII, CuII, ZnII, and CdII has been investigated in the solid state and in aqueous solution. Potentiometric measurements revealed a generally high stability for the bis complexes of the divalent cations with maximum stability for NiII (log beta2 = 21.2, beta2 = [M(dapi)2][M](-1)[dapi](-2), 25 degrees C, mu = 0.1 mol dm(-3)). Cyclic voltammetry established quasi-reversible formation of [Ni(dapi)2]3+ with a redox potential of 0.91 V (versus NHE) for the Ni(II/III) couple. [Co(dapi)2]3+ was prepared by aerial oxidation of the corresponding CoII precursor. The two isomers trans-[Co(dapi)2]3+ (1(3+), 26%) and cis-[Co(dapi)2]3+ (2(3+), 74%), have been separated and isolated as solid Cl- and CF3SO3- salts. In a non-aqueous medium 1(3+) and 2(3+) reacted with paraformaldehyde and NEt3 to give the methylidene-imino derivatives 3(3+) and 4(3+), in which the two piperidine rings are bridged by two or one N-CH2-O-CH2-N bridges, respectively. Crystal structure analyses were performed for H3dapi[ZnCl4]Cl, 1Cl3 x 2H2O, 2Cl3 x H2O, 3[ZnCl4]Cl, 4[ZnCl4]Cl, [Ni(dapi)2]Cl2 x H2O, [Cu(dapi)2](NO3)2, [Cu(dapi)Cl2], [(dapi)ClCd-(mu2-Cl)2-CdCl(dapi)], and [Co(dapi)(NO2)(CO3)]. The stability of [M(II)(dapi)]2+ and [M(II)(dapi)2]2+ complexes in aqueous solution, particularly the remarkably high tendency of [M(dapi)]2+ to undergo coordinative disproportionation is discussed in terms of the specific steric requirements of this ligand. Molecular mechanics calculations have been performed to analyze the different types of strain in these complexes. A variety of alkylated derivatives of dapi have been prepared by reductive alkylation with formaldehyde, benzaldehyde, salicylaldehyde, and pyridine-2-carbaldehyde. The NiII complexes of the pentadentate N3,N5-bis(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py2dapi) and the hexadentate N3,N5,1-tris(2-pyridinylmethyl)-cis-3,5-diaminopiperidine (py3dapi) have been isolated as crystalline ClO4- salts [Ni(py2dapi)Cl]ClO4 and [Ni(py3dapi)](ClO4)2 x H2O and characterized by crystal structure analyses.

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“…In 1977 Rielley et al reported that [(bpy)PtCl 2 ] reacts with cis,cis-1,3,5-triaminocyclohexane (tach) in air to form [(k 3tach À2 )Pt(bpy)(H 2 O)] 2 + (tach À2 = twice deprotonated tach). [87] In contrast a reaction of [(bpy)PtCl 2 ] with cis-1,3-diaminocyclohexane (dach) under the same conditions yielded the Pt II complex, [(k 2 -dach)Pt(bpy)] 2 + . This result suggested that a facially coordinating ligand might help promote aerobic oxidation of Pt II centers.…”

Section: Aerobic Oxidation Of Pt II Complexes To Pt Ivmentioning

confidence: 99%

Reactions of Pd and Pt Complexes with Molecular Oxygen

Scheuermann

Goldberg

2014

Chemistry A European J

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Knowledge of exactly how metal complexes react with molecular oxygen is still limited and this has hampered efforts to develop catalysts for oxidation reactions using O2 as the oxidant and/or oxygen-atom source. A better understanding of the reactions of different types of metal complexes with O2 will be of great utility in rational catalyst development. Reactions between molecular oxygen and Pd(0-II) and Pt(0-IV) complexes are reviewed here.

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Structural characterization of a novel platinum(IV) complex produced by deprotonation of coordinated amino groups of the rigid ligand cis,cis-1,3,5-triaminocyclohexane

Cited by 52 publications

References 2 publications

Structural and anticancer properties of hydrogen bonded diphenyl phosphate adducts of Pt(IV) complexes: The importance of pKa matching

Structural and anticancer properties of hydrogen bonded diphenyl phosphate adducts of Pt(IV) complexes: The importance of pKa matching

The Coordination Chemistry ofcis-3,5-Diaminopiperidine and Substituted Derivatives

Reactions of Pd and Pt Complexes with Molecular Oxygen

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