Azido complexes of nickel(II), palladium(II), and platinum(II)

Bowman, Kristin; Dori, Zvi

doi:10.1021/ic50084a049

Cited by 31 publications

(6 citation statements)

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“…Solvents were purchased from Aldrich and dried by the usual procedures. cis-[Pt(N 3 ) 2 (PPh 3 ) 2 ] 1 9e and cis-[Pt(N 3 ) 2 (2,2 -bipy)] 4 22 were prepared according to published procedures. C, H and N elemental analyses were carried out by the Microanalytical Service of the Instituto Superior Técnico, Lisbon.…”

Section: Experimental General Materials and Measurementsmentioning

confidence: 99%

Microwave synthesis of mono- and bis-tetrazolato complexes via 1,3-dipolar cycloaddition of organonitriles with platinum(ii)-bound azides

Mukhopadhyay¹,

Lasri²,

Charmier

et al. 2007

Dalton Trans.

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[2 + 3] Cycloaddition reactions of the diazidoplatinum(II) complexes cis-[Pt(N3)2(PPh3)2] 1 and cis-[Pt(N3)2(2,2'-bipy)] 4 with organonitriles NCR 2 give the bis(tetrazolato) complexes trans-[Pt(N4CR)2(PPh3)2] 3 [R = Me (3a), Et (3b), Pr (3c), Ph (3d), 4-ClC6H4 (3e)] and cis-[Pt(N4CR)2(2,2'-bipy)] 5 [R = Me (5a), Et (5b), Pr (5c), Ph (5d)]. The reaction of cis-[Pt(N3)2(PPh3)2] I with propionitrile also affords, apart from 3b, the unexpected mixed cyano-tetrazolato complex trans-[Pt(CN)(5-ethyltetrazolato)(PPh3)2] 3b' which is derived from the reaction of the bis(tetrazolato) 3b with propionitrile, with concomitant formation of 5-ethyl-1H-tetrazole, via a suggested unusual oxidative addition of the nitrile to PtII. All these reactions are greatly accelerated by microwave irradiation and this method also shows a higher selectivity in the case of the reaction of propionitrile with 1, leading only to the formation of 3b. All the complexes obtained were characterized by IR, 1H, 13C and 31P[1H] (for complexes 3) NMR spectroscopies, FAB-MS and elemental analyses. Complexes 3b', 3d, 3e and 5d were also characterized by X-ray structural analyses.

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Section: Experimental General Materials and Measurementsmentioning

confidence: 99%

Microwave synthesis of mono- and bis-tetrazolato complexes via 1,3-dipolar cycloaddition of organonitriles with platinum(ii)-bound azides

Mukhopadhyay¹,

Lasri²,

Charmier

et al. 2007

Dalton Trans.

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“…Ni(N 3 ) 2 L 2 (L = PMe 3 , PEt 3 ; L 2 = dppe) were prepared by the literature method. 23 2,6-Diethylphenyl isocyanide was prepared as described in the literature. 24…”

Section: Experimental General Materials and Measurementsmentioning

confidence: 99%

Synthesis, structures and properties of bis(carbodiimido) complexes of Ni(ii), Pd(ii) and Pt(ii)

Kim

Joo

Han

et al. 2002

J. Chem. Soc., Dalton Trans.

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“…Here we describe the synthesis and characterisation of new Pt IV azido complexes 4-6 and their synthetic Pt II precursors 1-3 (Fig. 1); although complexes 1 and 2 have been previously reported 18, 28 we present here further characterisation, including X-ray crystallographic structures.…”

Section: Introductionmentioning

confidence: 98%

Synthesis, characterisation and photochemistry of PtIV pyridyl azido acetato complexes

et al. 2009

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Pt II azido complexes [Pt(bpy) (N 3 ) 2 ] (1), [Pt(phen) (N 3 ) 2 ] (2) and trans-[Pt(N 3 ) 2 (py) 2 ] (3) incorporating the bidentate diimine ligands 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen) or the monodentate pyridine (py) respectively, have been synthesised from their chlorido precursors and characterised by x-ray crystallography; complex 3 shows significant deviation from squareplanar geometry (N 3 -Pt-N 3 angle 146.7°) as a result of steric congestion at the Pt centre. The novel Pt IV complexes trans, cis-[Pt(bpy)(OAc) 2 (N 3 ) 2 ] (4), trans, cis-[Pt(phen)(OAc) 2 (N 3 ) 2 ] (5), trans, trans, trans-[Pt(OAc) 2 (N 3 ) 2 (py) 2 ] (6), were obtained from 1-3 via oxidation with H 2 O 2 in acetic acid followed by reaction of the intermediate with acetic anhydride. Complexes 4-6 exhibit interesting structural and photochemical properties that were studied by x-ray, NMR and UV-vis spectroscopy and TDDFT. These Pt IV complexes exhibit greater absorption at longer wavelengths (ε = 9756 M −1 cm −1 at 315 nm for 4; ε = 796 M −1 cm −1 at 352 nm for 5; ε = 16900 M −1 cm −1 at 307 nm for 6, in aqueous solution) than previously reported Pt IV azide complexes, due to the presence of aromatic amines, and 4-6 undergo photoactivation with both UVA (365 nm) and visible green light (514 nm). The UV-vis spectra of complexes 4-6 were calculated using TD-DFT; the nature of the transitions contributing to the UV-vis bands provide insight into the mechanism of production of the observed photoproducts. The UV-vis spectra of 1-3 were also simulated by computational methods and comparison between Pt II and Pt IV electronic and structural properties allowed further elucidation of the photochemistry of 4-6.

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Azido complexes of nickel(II), palladium(II), and platinum(II)

Cited by 31 publications

References 1 publication

Microwave synthesis of mono- and bis-tetrazolato complexes via 1,3-dipolar cycloaddition of organonitriles with platinum(ii)-bound azides

Microwave synthesis of mono- and bis-tetrazolato complexes via 1,3-dipolar cycloaddition of organonitriles with platinum(ii)-bound azides

Synthesis, structures and properties of bis(carbodiimido) complexes of Ni(ii), Pd(ii) and Pt(ii)

Synthesis, characterisation and photochemistry of PtIV pyridyl azido acetato complexes

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