Axial Functionalization of Sterically Hindered Titanium Phthalocyanines

Several axially functionalized, weakly aggregating titanium phthalocyanines (Pc) have been synthesized and characterized. Soluble titanium dichlorido tetrakis-(1,1,4,4-tetramethyl-6,7-tetralino)-porphyrazine [Pc^#TiCl₂] (<b>5</b>) has been prepared by reductive cyclotetramerization of the respective dinitrile precursor in the presence of TiCl₄. <b>5</b> and the analogous oxido compound [Pc^#TiO] (<b>1</b>) are versatile starting materials for the formation of other axially functionalized titanium phthalocyanines such as organoimido (<b>6</b>, <b>7</b>), alkoxido and aryloxido (<b>8</b>, <b>9</b>), peroxido (<b>10</b>), sulfido (<b>12</b>), disulfido (<b>11</b>), selenido (<b>14</b>) or diselenido (<b>13</b>) species. Furthermore the deprotonated ligand salts [Pc^#M₂] (M = Li (<b>2</b>), Na (<b>3</b>), K (<b>4</b>) are described. The reactivity of the titanium compounds was studied in atom group transfer reactions and ethene polymerization. The crystal structures of <b>5</b> and the free ligand Pc^#H₂ are reported. <b>5</b> crystallizes from dichloromethane in the cubic space group <i>Im</i>3̅. The two chlorido ligands exhibit a cis arrangement. The free ligand Pc^#H₂ crystallizes in the trigonal space group <i>R</i>3̅

Axial Functionalization of Sterically Hindered Titanium Phthalocyanines

Several axially functionalized, weakly aggregating titanium phthalocyanines (Pc) have been synthesized and characterized. Soluble titanium dichlorido tetrakis-(1,1,4,4-tetramethyl-6,7-tetralino)-porphyrazine [Pc^#TiCl₂] (<b>5</b>) has been prepared by reductive cyclotetramerization of the respective dinitrile precursor in the presence of TiCl₄. <b>5</b> and the analogous oxido compound [Pc^#TiO] (<b>1</b>) are versatile starting materials for the formation of other axially functionalized titanium phthalocyanines such as organoimido (<b>6</b>, <b>7</b>), alkoxido and aryloxido (<b>8</b>, <b>9</b>), peroxido (<b>10</b>), sulfido (<b>12</b>), disulfido (<b>11</b>), selenido (<b>14</b>) or diselenido (<b>13</b>) species. Furthermore the deprotonated ligand salts [Pc^#M₂] (M = Li (<b>2</b>), Na (<b>3</b>), K (<b>4</b>) are described. The reactivity of the titanium compounds was studied in atom group transfer reactions and ethene polymerization. The crystal structures of <b>5</b> and the free ligand Pc^#H₂ are reported. <b>5</b> crystallizes from dichloromethane in the cubic space group <i>Im</i>3̅. The two chlorido ligands exhibit a cis arrangement. The free ligand Pc^#H₂ crystallizes in the trigonal space group <i>R</i>3̅

Axial Functionalization of Sterically Hindered Titanium Phthalocyanines

Several axially functionalized, weakly aggregating titanium phthalocyanines (Pc) have been synthesized and characterized. Soluble titanium dichlorido tetrakis-(1,1,4,4-tetramethyl-6,7-tetralino)-porphyrazine [Pc^#TiCl₂] (<b>5</b>) has been prepared by reductive cyclotetramerization of the respective dinitrile precursor in the presence of TiCl₄. <b>5</b> and the analogous oxido compound [Pc^#TiO] (<b>1</b>) are versatile starting materials for the formation of other axially functionalized titanium phthalocyanines such as organoimido (<b>6</b>, <b>7</b>), alkoxido and aryloxido (<b>8</b>, <b>9</b>), peroxido (<b>10</b>), sulfido (<b>12</b>), disulfido (<b>11</b>), selenido (<b>14</b>) or diselenido (<b>13</b>) species. Furthermore the deprotonated ligand salts [Pc^#M₂] (M = Li (<b>2</b>), Na (<b>3</b>), K (<b>4</b>) are described. The reactivity of the titanium compounds was studied in atom group transfer reactions and ethene polymerization. The crystal structures of <b>5</b> and the free ligand Pc^#H₂ are reported. <b>5</b> crystallizes from dichloromethane in the cubic space group <i>Im</i>3̅. The two chlorido ligands exhibit a cis arrangement. The free ligand Pc^#H₂ crystallizes in the trigonal space group <i>R</i>3̅

Axial Functionalization of Sterically Hindered Titanium Phthalocyanines

Several axially functionalized, weakly aggregating titanium phthalocyanines (Pc) have been synthesized and characterized. Soluble titanium dichlorido tetrakis-(1,1,4,4-tetramethyl-6,7-tetralino)-porphyrazine [Pc^#TiCl₂] (<b>5</b>) has been prepared by reductive cyclotetramerization of the respective dinitrile precursor in the presence of TiCl₄. <b>5</b> and the analogous oxido compound [Pc^#TiO] (<b>1</b>) are versatile starting materials for the formation of other axially functionalized titanium phthalocyanines such as organoimido (<b>6</b>, <b>7</b>), alkoxido and aryloxido (<b>8</b>, <b>9</b>), peroxido (<b>10</b>), sulfido (<b>12</b>), disulfido (<b>11</b>), selenido (<b>14</b>) or diselenido (<b>13</b>) species. Furthermore the deprotonated ligand salts [Pc^#M₂] (M = Li (<b>2</b>), Na (<b>3</b>), K (<b>4</b>) are described. The reactivity of the titanium compounds was studied in atom group transfer reactions and ethene polymerization. The crystal structures of <b>5</b> and the free ligand Pc^#H₂ are reported. <b>5</b> crystallizes from dichloromethane in the cubic space group <i>Im</i>3̅. The two chlorido ligands exhibit a cis arrangement. The free ligand Pc^#H₂ crystallizes in the trigonal space group <i>R</i>3̅

Soluble Molybdenum(V) Imido Phthalocyanines and Pyrazinoporphyrazines: Crystal Structure, UV–vis and Electron Paramagnetic Resonance Spectroscopic Studies

Soluble alkyl and aryl imido phthalocyanines [Pc^#Mo­(NR)­Cl] (R = <i>t</i>Bu, Mes) with molybdenum­(V) as central metal were prepared and studied by UV–vis and electron paramagnetic resonance (EPR) spectroscopy. As structural analogue to the weakly aggregating, soluble alkyl substituted Pc^# ligand, a new, more electron deficient octaazaphthalocyanine, the pyrazinoporphyrazine ligand Ppz^#, was designed. The respective alkyl and aryl imido complexes [Ppz^#Mo­(NR)­Cl] are the first examples of molybdenum pyrazinoporphyrazines. UV–vis and EPR spectra revealed unexpected differences between the alkyl and the aryl imido complexes, indicating different electronic structures depending on the nature of the axial ligand. The octahedral coordination of the molybdenum atoms by the axial NR and Cl ligands and the equatorial macrocycles could be verified by EPR spectroscopy. This result was also confirmed by the crystal structure of [Pc^#Mo­(NMes)­Cl], which crystallizes from CH₂Cl₂ in the cubic space group <i>Im</i>3̅