EPR and absorption spectra of singly reduced mono- and dinuclear diorganoplatinum complexes of heterocyclic .alpha.-diimines

Braterman, Paul S.; Song, Jae Inh; Vogler, Conny; Kaim, Wolfgang

doi:10.1021/ic00028a018

Cited by 60 publications

(26 citation statements)

References 4 publications

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“…Such an elongation has previously been observed for other metal complexes containing such azo ligands. [20] In agreement with this back-donation, the N2-C5 distances [1.410 (18) and 1.385 Å for 1 and 2, respectively] are shorter than the N1-C6 distances [1.449 (19) and 1.444(11) Å for 1 and 2, respectively] for both complexes. Averaging out of bond lengths inside a chelate ring after metalation is a typical feature of metal complexes containing azo ligands.…”

Section: Synthesis and Structuressupporting

confidence: 66%

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Structures, Redox and Spectroscopic Properties of Pd^II and Pt^II Complexes Containing an Azo Functionality

2009

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The complexes [PdCl 2 (pap)] (1) and [PtCl 2 (pap)] (2; pap = 2-phenylazopyridine) were synthesized by treating PdCl 2 or K 2 PtCl 4 , respectively, with pap and characterized by 1 H NMR spectroscopy and elemental analysis. Both these complexes, together with the previously reported complex [(az)Pd(µ-Cl) 2 -Pd(az)] (3; az = azobenzene), were also characterized by Xray crystallography. The structures of 1, 2, and 3 show a slightly elongated N-N azo double bond due to back-donation from the metal centers and a twisting of the uncoordinated part of the ligands with respect to the rest of the molecule. Cyclic voltammetry of 1, 2, 3, and the related complex

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Section: Synthesis and Structuressupporting

confidence: 66%

“…[14][15][16][17] Although complexes of PtCl 2 and PdCl 2 have been studied with a variety of nitrogen-containing π-acceptor ligands, [18,19] there are very few reports of such complexes with ligands containing an azo group. [15,16,20] The ligand 2-phenylazopyridine (pap) has often been used in coordination chemistry.…”

Section: Introductionmentioning

confidence: 99%

Structures, Redox and Spectroscopic Properties of Pd^II and Pt^II Complexes Containing an Azo Functionality

2009

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“…= 2.020 and g k = 1.974 ( Figure 1D). [36,37] Noticeably,n oc oupling to the 195 Pt nucleus (I = 1/2, 33.8 %abundant) is resolved, suggesting that minimal spin density resides at the Pt 3 core. [33][34][35] However,they are very much in accord with spectra exhibited by systems containing closed-shell platinum centers bound to radical ligands.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…[33][34][35] However,they are very much in accord with spectra exhibited by systems containing closed-shell platinum centers bound to radical ligands. [36,37] Noticeably,n oc oupling to the 195 Pt nucleus (I = 1/2, 33.8 %abundant) is resolved, suggesting that minimal spin density resides at the Pt 3 core.…”

Section: Angewandte Chemiementioning

confidence: 99%

Monomeric Chini‐Type Triplatinum Clusters Featuring Dianionic and Radical‐Anionic π*‐Systems

2016

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Owing to their unique topologies and abilities to selfassemble into av ariety of extended and aggregated structures, the binary platinum carbonyl clusters [Pt 3 (CO) 6 ] n 2À ("Chini clusters") continue to draw significant interest. Herein, we report the isolation and structural characterization of the trinuclear electron-transfer series [Pt 3 (m-CO) 3 (CNAr Dipp2 ) 3 ] nÀ (n = 0, 1, 2), which represents au nique set of monomeric Pt 3 clusters supported by p-acidic ligands.S pectroscopic,c omputational, and synthetic investigations demonstrate that the highest-occupied molecular orbitals of the mono-and dianionic clusters consist of acombined p*-framework of the CO and CNAr Dipp2 ligands,w ith negligible Pt character.A ccordingly,t his study provides precedent for an ensemble of carbonyl and isocyanide ligands to function in ar edox noninnocent manner.

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“…Reduction of the free ligand bipyridine under the same conditions yields a very similar spectrum with the maxima at 1222 nm (e = 280 M ±1 cm ±1 ), 580 nm (2410), and 392 nm (11800). They can be assigned to symmetry forbidden transitions from the single-occupied molecular orbital (SOMO, b 1 -symmetry) to higher lying unoccupied molecular orbitals: Band 1 (maximum at k 5 in Table 3): SOMO (b 1 ) ± LUMO + 1 (a 2 ), Band 2 (k 3 ): SOMO (b 1 ) ± LUMO + 2 (a 2 ), Band 3 (k 2 ): SOMO (b 1 ) ± LUMO + 3 (a 2 ) [24,25] and a similar assignment for the reduced nickel complex is reasonable. Interestingly the extinction coefficients of Bands 1 and 2 found for the radical anion complex are higher than those for the free [bpy]´± whereas Band 3 of the latter shows higher intensity.…”

Section: Spectroscopy On the Parent And Reduced States Of [(Bpy)nimesmentioning

confidence: 99%

Synthesis, Spectroscopic Properties, and Crystal Structure of 2,2′-Bipyridyldimesitylnickel(II)

Klein

2001

Z. anorg. allg. Chem.

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The dimesitylnickel(II) complex [(bpy)NiMes 2 ] (Mes = mesityl = 2,4,6-trimethylphenyl) was prepared and examined spectroscopically and electrochemically. The crystal and molecular structure was determined from single crystal X-Ray diffraction experiments (monoclinic, P2 1 /n, Z = 4, a = 8.3092(8) A Ê , b = 18.233(2) A Ê , c = 15.226(2) A Ê , b = 98.035(6)°). The nickel atom displays a distorted square planar environment. The axial positions of the square plane are shielded by each one of the methyl groups on the mesityl substituents. The complex shows electrochemical reduction processes that are mainly centered on the bpy ligand as inferred from spectroelectrochemical investigations (EPR and UV/Vis/NIR absorption) of the radical anion or dianion. The observed oxidation is assigned to a Ni II /Ni III couple. The title complex exhibits strongly solvatochromic longwavelength electronic absorptions.Synthese, Spektroskopische Eigenschaften und Moleku È lstruktur von 2,2'-Bipyridindimesitylnickel(II) Inhaltsu È bersicht. Der Dimesitylnickel(II) Komplex [(bpy)NiMes 2 ] (Mes = Mesityl = 2,4,6-Trimethylphenyl, bpy = 2,2'-Bipyridin) wurde synthetisiert und seine spektroskopischen sowie elektrochemischen Eigenschaften studiert. Die Kristallund Moleku È lstruktur konnte durch Ro È ntgenbeugung an einem Einkristall ermittelt werden (monoklin, P2 1 /n, Z = 4, a = 8.3092(8) A Ê , b = 18.233(2) A Ê , c = 15.226(2) A Ê , b = 98.035(6)°). Das Nickelatom zeigt eine verzerrt quadratisch planare Umgebung. Die axialen Positionen des Zentralatoms werden von je einer Methylgruppe an den beiden Mesitylsubstituenten sterisch abgeschirmt. Die Verbindung la È sst sich in zwei reversiblen Ein-Elektronenschritten reduzieren, wobei die Elektronen in Orbitale eingelagert werden, die hauptsa È chlich im Bipyridinliganden lokalisiert sind, wie mit Hilfe von spektroelektrochemischen Untersuchungen (EPR und UV/ Vis/NIR Absorption) ermittelt werden konnte. Die ebenfalls beobachtete elektrochemische Ein-Elektronen Oxidation ist einem Ni II /Ni III Redoxpaar zuzuordnen. Die Verbindung zeigt eine sehr starke Solvatochromie ihrer langwelligsten Absorption.

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EPR and absorption spectra of singly reduced mono- and dinuclear diorganoplatinum complexes of heterocyclic .alpha.-diimines

Cited by 60 publications

References 4 publications

Structures, Redox and Spectroscopic Properties of Pd^II and Pt^II Complexes Containing an Azo Functionality

Structures, Redox and Spectroscopic Properties of Pd^II and Pt^II Complexes Containing an Azo Functionality

Monomeric Chini‐Type Triplatinum Clusters Featuring Dianionic and Radical‐Anionic π*‐Systems

Synthesis, Spectroscopic Properties, and Crystal Structure of 2,2′-Bipyridyldimesitylnickel(II)

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EPR and absorption spectra of singly reduced mono- and dinuclear diorganoplatinum complexes of heterocyclic .alpha.-diimines

Cited by 60 publications

References 4 publications

Structures, Redox and Spectroscopic Properties of PdII and PtII Complexes Containing an Azo Functionality

Structures, Redox and Spectroscopic Properties of PdII and PtII Complexes Containing an Azo Functionality

Monomeric Chini‐Type Triplatinum Clusters Featuring Dianionic and Radical‐Anionic π*‐Systems

Synthesis, Spectroscopic Properties, and Crystal Structure of 2,2′-Bipyridyldimesitylnickel(II)

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Structures, Redox and Spectroscopic Properties of Pd^II and Pt^II Complexes Containing an Azo Functionality

Structures, Redox and Spectroscopic Properties of Pd^II and Pt^II Complexes Containing an Azo Functionality