Synthesis and Structure of Monomeric and Platinum-Bonded (1,10-Phenanthroline)thallium Complexes

Abstract

Keywords: MetalϪmetal interactions / Platinum / Thallium / N ligands / NMR spectroscopyOxidative addition of (1,10-phenanthroline)thallium(III) complexes [Tl(phen) n (solv)] 3+ (n = 1−2) (phen = 1,10-phenanthroline) to [Pt(CN) 4 ] 2− in DMSO, in the presence of cyanide ions and in the absence of cyanide ions yielded heterodinuclear metal−metal-bonded complexes, [(NC) 5 Pt−Tl(phen) n (solv)] and [(NC) 4 Pt−Tl(phen) n (solv)] + (n = 0, 1, and 2), respectively. The presence of a direct Pt−Tl bond in the complex is evident by a very strong one-bond 195 Pt− 205 Tl spin-spin coupling detected by 205 Tl NMR: 1 J = 94.0 kHz (1a), 84.2 kHz (2a), and 77.1 kHz (3a) corresponding to n = 0, 1, and 2 in [(NC) 4 Pt−Tl(phen) n (solv)] + , and 1 J = 65.4 kHz (2b) and 62.5 kHz (3b) for n = 1 and 2, respectively, in [(NC) 5 Pt− Tl(phen) n (solv)]. The crystal structures of [(NC) 5 Pt−Tl-[a]

Structure Lattice-Dimensionality and Spectroscopic Property Correlations in Novel Binary and Ternary Materials of Group 13 Elements with α-Hydroxycarboxylic Benzilic Acid and Phenanthroline

“…These values are very similar to related Tl−O bond lengths reported previously, 57,58 60 The increase in the Tl−N bond lengths in the investigated compound is compatible with the low thallium oxidation state. 60 There are no hydrogen bonds in the lattice of 6.…”

Structure Lattice-Dimensionality and Spectroscopic Property Correlations in Novel Binary and Ternary Materials of Group 13 Elements with α-Hydroxycarboxylic Benzilic Acid and Phenanthroline

“…These values are very similar to related Tl−O bond lengths reported previously, 57,58 60 The increase in the Tl−N bond lengths in the investigated compound is compatible with the low thallium oxidation state. 60 There are no hydrogen bonds in the lattice of 6.…”

Luminescent One- And Two-Dimensional Extended Structures and a Loosely Associated Dimer Based on Platinum(II)–Thallium(I) Backbones

“…Later works have shown that emission bands cover a wide range (444–700 nm), depending on the compound. Platinum−thallium polynuclear complexes are also interesting because of their structural and other spectroscopic ( 195 Pt NMR) properties. ,,– Four types of bonding situations have been observed, depending on the formal oxidation state of metal centers: (Pt 0 −Tl I ), ,– ,– (Pt II −Tl I ), – ,,,,,,– (Pt II −Tl II ), and (Pt II −Tl III ), ,,– ,– although in most cases, particularly in the latter ones, electronic redistribution makes it difficult, if not impossible, to assign oxidation states.…”

Modification of Binuclear Pt−Tl Bonded Complexes by Attaching Bipyridine Ligands to the Thallium Site

“…0.04 Å) than the two cis bonds, Pt−C2 and Pt−C3 (Table ). A similar, and even more pronounced, trans lengthening effect was observed in the structure of a symmetry-related compound, [(NC) 5 Pt−Tl(en) 2 ], with an axial Pt−C distance exceeding the equatorial ones by more than 0.07 Å 6b. This is assumed to be due to the trans influence of the X ligand in the pseudooctahedral complex [(NC) 5 Pt−X]; this effect is well-known for a large number of σ-bonded complexes of transition metals …”

“…Similarly to the previously studied family of complexes [(NC) 5 Pt−Tl(CN) n (aq)] n - ( n = 0−3) in an aqueous medium,3b and [(NC) 5 Pt−Tl(solv)] and [(NC) 5 Pt−Tl(en) m (solv)] ( m = 1, 2) species in dimethyl sulfoxide solution,6b the bimetallic Pt−Tl−bipy compounds in dmso exhibit very large values of one-bond 195 Pt− 205 Tl spin−spin coupling constants (Table ). This strong coupling is a characteristic feature of the bonding between the two metals with the formal oxidation states {Pt II- Tl III }, and is an indication of a significant contribution of thallium 6s orbitals to the metal−metal bonding 3b.…”

“…The main structural feature of these bimetallic compounds is certainly the very short and unbuttressed Pt−Tl bond: 2.6187(7) and 2.6117(5) Å for compounds 2 and 3 , respectively. The distances fall into the range of values obtained for the family of related compounds, all containing [(NC) 5 Pt−Tl(L) m ] (L = ligand) entities with a variety of ligands coordinated to the thallium site: [(NC) 5 Pt−Tl(CN) n (aq)] n - ( n = 0−3; Pt−Tl = 2.598−2.638 Å), 3c,d [(NC) 5 Pt−Tl(dmso) 4 ] (Pt−Tl = 2.613 Å),6b [(NC) 5 Pt−Tl(en) 2 ] (Pt−Tl = 2.635 Å),6b and [(NC) 5 Pt−Tl(phen) m (solv)] ( m = 1, 2; solv = dmso; Pt−Tl = 2.630−2.638 Å) 6c. The differences in the metal−metal separations are attributed to the composition and to the geometry of the thallium coordination environment in the complexes.…”

Structure Lattice-Dimensionality and Spectroscopic Property Correlations in Novel Binary and Ternary Materials of Group 13 Elements with α-Hydroxycarboxylic Benzilic Acid and Phenanthroline

“…These values are very similar to related Tl−O bond lengths reported previously, 57,58 60 The increase in the Tl−N bond lengths in the investigated compound is compatible with the low thallium oxidation state. 60 There are no hydrogen bonds in the lattice of 6.…”

Luminescent One- And Two-Dimensional Extended Structures and a Loosely Associated Dimer Based on Platinum(II)–Thallium(I) Backbones

“…Later works have shown that emission bands cover a wide range (444–700 nm), depending on the compound. Platinum−thallium polynuclear complexes are also interesting because of their structural and other spectroscopic ( 195 Pt NMR) properties. ,,– Four types of bonding situations have been observed, depending on the formal oxidation state of metal centers: (Pt 0 −Tl I ), ,– ,– (Pt II −Tl I ), – ,,,,,,– (Pt II −Tl II ), and (Pt II −Tl III ), ,,– ,– although in most cases, particularly in the latter ones, electronic redistribution makes it difficult, if not impossible, to assign oxidation states.…”

Modification of Binuclear Pt−Tl Bonded Complexes by Attaching Bipyridine Ligands to the Thallium Site

“…0.04 Å) than the two cis bonds, Pt−C2 and Pt−C3 (Table ). A similar, and even more pronounced, trans lengthening effect was observed in the structure of a symmetry-related compound, [(NC) 5 Pt−Tl(en) 2 ], with an axial Pt−C distance exceeding the equatorial ones by more than 0.07 Å 6b. This is assumed to be due to the trans influence of the X ligand in the pseudooctahedral complex [(NC) 5 Pt−X]; this effect is well-known for a large number of σ-bonded complexes of transition metals …”

“…Similarly to the previously studied family of complexes [(NC) 5 Pt−Tl(CN) n (aq)] n - ( n = 0−3) in an aqueous medium,3b and [(NC) 5 Pt−Tl(solv)] and [(NC) 5 Pt−Tl(en) m (solv)] ( m = 1, 2) species in dimethyl sulfoxide solution,6b the bimetallic Pt−Tl−bipy compounds in dmso exhibit very large values of one-bond 195 Pt− 205 Tl spin−spin coupling constants (Table ). This strong coupling is a characteristic feature of the bonding between the two metals with the formal oxidation states {Pt II- Tl III }, and is an indication of a significant contribution of thallium 6s orbitals to the metal−metal bonding 3b.…”

“…The main structural feature of these bimetallic compounds is certainly the very short and unbuttressed Pt−Tl bond: 2.6187(7) and 2.6117(5) Å for compounds 2 and 3 , respectively. The distances fall into the range of values obtained for the family of related compounds, all containing [(NC) 5 Pt−Tl(L) m ] (L = ligand) entities with a variety of ligands coordinated to the thallium site: [(NC) 5 Pt−Tl(CN) n (aq)] n - ( n = 0−3; Pt−Tl = 2.598−2.638 Å), 3c,d [(NC) 5 Pt−Tl(dmso) 4 ] (Pt−Tl = 2.613 Å),6b [(NC) 5 Pt−Tl(en) 2 ] (Pt−Tl = 2.635 Å),6b and [(NC) 5 Pt−Tl(phen) m (solv)] ( m = 1, 2; solv = dmso; Pt−Tl = 2.630−2.638 Å) 6c. The differences in the metal−metal separations are attributed to the composition and to the geometry of the thallium coordination environment in the complexes.…”

Structure Lattice-Dimensionality and Spectroscopic Property Correlations in Novel Binary and Ternary Materials of Group 13 Elements with α-Hydroxycarboxylic Benzilic Acid and Phenanthroline

“…These values are very similar to related Tl−O bond lengths reported previously, 57,58 60 The increase in the Tl−N bond lengths in the investigated compound is compatible with the low thallium oxidation state. 60 There are no hydrogen bonds in the lattice of 6.…”

Luminescent One- And Two-Dimensional Extended Structures and a Loosely Associated Dimer Based on Platinum(II)–Thallium(I) Backbones

“…Later works have shown that emission bands cover a wide range (444–700 nm), depending on the compound. Platinum−thallium polynuclear complexes are also interesting because of their structural and other spectroscopic ( 195 Pt NMR) properties. ,,– Four types of bonding situations have been observed, depending on the formal oxidation state of metal centers: (Pt 0 −Tl I ), ,– ,– (Pt II −Tl I ), – ,,,,,,– (Pt II −Tl II ), and (Pt II −Tl III ), ,,– ,– although in most cases, particularly in the latter ones, electronic redistribution makes it difficult, if not impossible, to assign oxidation states.…”

Modification of Binuclear Pt−Tl Bonded Complexes by Attaching Bipyridine Ligands to the Thallium Site

“…0.04 Å) than the two cis bonds, Pt−C2 and Pt−C3 (Table ). A similar, and even more pronounced, trans lengthening effect was observed in the structure of a symmetry-related compound, [(NC) 5 Pt−Tl(en) 2 ], with an axial Pt−C distance exceeding the equatorial ones by more than 0.07 Å 6b. This is assumed to be due to the trans influence of the X ligand in the pseudooctahedral complex [(NC) 5 Pt−X]; this effect is well-known for a large number of σ-bonded complexes of transition metals …”

“…Similarly to the previously studied family of complexes [(NC) 5 Pt−Tl(CN) n (aq)] n - ( n = 0−3) in an aqueous medium,3b and [(NC) 5 Pt−Tl(solv)] and [(NC) 5 Pt−Tl(en) m (solv)] ( m = 1, 2) species in dimethyl sulfoxide solution,6b the bimetallic Pt−Tl−bipy compounds in dmso exhibit very large values of one-bond 195 Pt− 205 Tl spin−spin coupling constants (Table ). This strong coupling is a characteristic feature of the bonding between the two metals with the formal oxidation states {Pt II- Tl III }, and is an indication of a significant contribution of thallium 6s orbitals to the metal−metal bonding 3b.…”

“…The main structural feature of these bimetallic compounds is certainly the very short and unbuttressed Pt−Tl bond: 2.6187(7) and 2.6117(5) Å for compounds 2 and 3 , respectively. The distances fall into the range of values obtained for the family of related compounds, all containing [(NC) 5 Pt−Tl(L) m ] (L = ligand) entities with a variety of ligands coordinated to the thallium site: [(NC) 5 Pt−Tl(CN) n (aq)] n - ( n = 0−3; Pt−Tl = 2.598−2.638 Å), 3c,d [(NC) 5 Pt−Tl(dmso) 4 ] (Pt−Tl = 2.613 Å),6b [(NC) 5 Pt−Tl(en) 2 ] (Pt−Tl = 2.635 Å),6b and [(NC) 5 Pt−Tl(phen) m (solv)] ( m = 1, 2; solv = dmso; Pt−Tl = 2.630−2.638 Å) 6c. The differences in the metal−metal separations are attributed to the composition and to the geometry of the thallium coordination environment in the complexes.…”