Metal Complexes of Hemilabile Ligands. Reactivity and Structure of Dichlorobis (o-(dipheny lphosphino) anisole) ruthenium (II)

John C. Jeffrey, Thomas Rauchfuss

Research output: Contribution to journalArticle

Abstract

The red complex RuCl2(PO)2 (1) (PO = o-(diphenylphosphino)anisole) crystallizes from dichloromethane/hexane as a solvate, RuCl2(PO)2·CH2Cl2, and has been characterized by a single-crystal X-ray structural analysis. The crystals have space group P21/n with a = 11.194 (1) Å, b = 28.294 (4) Å, c = 12.458 (1) Å, β = 95.50 (1)°, Z = 4, ρobsd = 1.40 g/cm3. and ρcaled = 1.40 g/cm3. The complex is six-coordinate with trans chlorine and cis phosphorus donor atoms. The Ru-P distances of 2.217 (1) and 2.219 (1) Å, are similar to those found for apical phosphines in square-pyramidal ruthenium(II) complexes. The Ru-O distances of 2.299 (3) and 2.257 (3) Å are greater than that of the sum of the respective covalent radii, consistent with a weak Ru-O bond. 1 undergoes reversible electrochemical oxidation in acetone at 0.778 V vs. Ag/AgCl and chemical oxidation with NOBF4 to afford the paramagnetic complex [RuCl2(PO)2](BF4) (2), characterized by its ESR spectrum. The room-temperature reaction of 1 with CO gives initially a fluxional monomeric complex, RuCl2(PO)2(CO) (4), and then all-trans-RuCl2(PO)2(CO)2 (3), via dissociation of the Ru-O bonds. Reaction of 1 with CO at elevated temperatures gives a new cis-dicarbonyl isomer. RuCl2(PO)2(CO)2 (5), which has trans phosphines. Unlike 4, complex 5 does not readily lose CO thermally; however, it is photochemically converted to a mixture of 3 and 4. Closely related reactions are observed when 1 is treated with tert-butyl isocyanide and the species RuCl2(PO)2(t-BuNC)2 (6) and RuCl2(PO)2(t-BuNC) (7) were identified spectroscopically (and isolated for 6). A reaction scheme rationalizing the formation of 3, 4, 5, 6, and 7 is presented and the results are discussed in light of the known work on phosphinoanisole-transition-metal complexes.

Original languageEnglish (US)
Pages (from-to)2658-2666
Number of pages9
JournalInorganic Chemistry
Volume18
Issue number10
DOIs
StatePublished - Jan 1 1979

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anisole
Ruthenium
Coordination Complexes
ruthenium
Carbon Monoxide
reactivity
Ligands
ligands
phosphines
metals
Phosphines
electrochemical oxidation
structural analysis
acetone
chlorine
phosphorus
isomers
transition metals
dissociation
Electrochemical oxidation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Metal Complexes of Hemilabile Ligands. Reactivity and Structure of Dichlorobis (o-(dipheny lphosphino) anisole) ruthenium (II). / Jeffrey, John C.; Rauchfuss, Thomas.

In: Inorganic Chemistry, Vol. 18, No. 10, 01.01.1979, p. 2658-2666.

Research output: Contribution to journalArticle

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title = "Metal Complexes of Hemilabile Ligands. Reactivity and Structure of Dichlorobis (o-(dipheny lphosphino) anisole) ruthenium (II)",
abstract = "The red complex RuCl2(PO)2 (1) (PO = o-(diphenylphosphino)anisole) crystallizes from dichloromethane/hexane as a solvate, RuCl2(PO)2·CH2Cl2, and has been characterized by a single-crystal X-ray structural analysis. The crystals have space group P21/n with a = 11.194 (1) {\AA}, b = 28.294 (4) {\AA}, c = 12.458 (1) {\AA}, β = 95.50 (1)°, Z = 4, ρobsd = 1.40 g/cm3. and ρcaled = 1.40 g/cm3. The complex is six-coordinate with trans chlorine and cis phosphorus donor atoms. The Ru-P distances of 2.217 (1) and 2.219 (1) {\AA}, are similar to those found for apical phosphines in square-pyramidal ruthenium(II) complexes. The Ru-O distances of 2.299 (3) and 2.257 (3) {\AA} are greater than that of the sum of the respective covalent radii, consistent with a weak Ru-O bond. 1 undergoes reversible electrochemical oxidation in acetone at 0.778 V vs. Ag/AgCl and chemical oxidation with NOBF4 to afford the paramagnetic complex [RuCl2(PO)2](BF4) (2), characterized by its ESR spectrum. The room-temperature reaction of 1 with CO gives initially a fluxional monomeric complex, RuCl2(PO)2(CO) (4), and then all-trans-RuCl2(PO)2(CO)2 (3), via dissociation of the Ru-O bonds. Reaction of 1 with CO at elevated temperatures gives a new cis-dicarbonyl isomer. RuCl2(PO)2(CO)2 (5), which has trans phosphines. Unlike 4, complex 5 does not readily lose CO thermally; however, it is photochemically converted to a mixture of 3 and 4. Closely related reactions are observed when 1 is treated with tert-butyl isocyanide and the species RuCl2(PO)2(t-BuNC)2 (6) and RuCl2(PO)2(t-BuNC) (7) were identified spectroscopically (and isolated for 6). A reaction scheme rationalizing the formation of 3, 4, 5, 6, and 7 is presented and the results are discussed in light of the known work on phosphinoanisole-transition-metal complexes.",
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N2 - The red complex RuCl2(PO)2 (1) (PO = o-(diphenylphosphino)anisole) crystallizes from dichloromethane/hexane as a solvate, RuCl2(PO)2·CH2Cl2, and has been characterized by a single-crystal X-ray structural analysis. The crystals have space group P21/n with a = 11.194 (1) Å, b = 28.294 (4) Å, c = 12.458 (1) Å, β = 95.50 (1)°, Z = 4, ρobsd = 1.40 g/cm3. and ρcaled = 1.40 g/cm3. The complex is six-coordinate with trans chlorine and cis phosphorus donor atoms. The Ru-P distances of 2.217 (1) and 2.219 (1) Å, are similar to those found for apical phosphines in square-pyramidal ruthenium(II) complexes. The Ru-O distances of 2.299 (3) and 2.257 (3) Å are greater than that of the sum of the respective covalent radii, consistent with a weak Ru-O bond. 1 undergoes reversible electrochemical oxidation in acetone at 0.778 V vs. Ag/AgCl and chemical oxidation with NOBF4 to afford the paramagnetic complex [RuCl2(PO)2](BF4) (2), characterized by its ESR spectrum. The room-temperature reaction of 1 with CO gives initially a fluxional monomeric complex, RuCl2(PO)2(CO) (4), and then all-trans-RuCl2(PO)2(CO)2 (3), via dissociation of the Ru-O bonds. Reaction of 1 with CO at elevated temperatures gives a new cis-dicarbonyl isomer. RuCl2(PO)2(CO)2 (5), which has trans phosphines. Unlike 4, complex 5 does not readily lose CO thermally; however, it is photochemically converted to a mixture of 3 and 4. Closely related reactions are observed when 1 is treated with tert-butyl isocyanide and the species RuCl2(PO)2(t-BuNC)2 (6) and RuCl2(PO)2(t-BuNC) (7) were identified spectroscopically (and isolated for 6). A reaction scheme rationalizing the formation of 3, 4, 5, 6, and 7 is presented and the results are discussed in light of the known work on phosphinoanisole-transition-metal complexes.

AB - The red complex RuCl2(PO)2 (1) (PO = o-(diphenylphosphino)anisole) crystallizes from dichloromethane/hexane as a solvate, RuCl2(PO)2·CH2Cl2, and has been characterized by a single-crystal X-ray structural analysis. The crystals have space group P21/n with a = 11.194 (1) Å, b = 28.294 (4) Å, c = 12.458 (1) Å, β = 95.50 (1)°, Z = 4, ρobsd = 1.40 g/cm3. and ρcaled = 1.40 g/cm3. The complex is six-coordinate with trans chlorine and cis phosphorus donor atoms. The Ru-P distances of 2.217 (1) and 2.219 (1) Å, are similar to those found for apical phosphines in square-pyramidal ruthenium(II) complexes. The Ru-O distances of 2.299 (3) and 2.257 (3) Å are greater than that of the sum of the respective covalent radii, consistent with a weak Ru-O bond. 1 undergoes reversible electrochemical oxidation in acetone at 0.778 V vs. Ag/AgCl and chemical oxidation with NOBF4 to afford the paramagnetic complex [RuCl2(PO)2](BF4) (2), characterized by its ESR spectrum. The room-temperature reaction of 1 with CO gives initially a fluxional monomeric complex, RuCl2(PO)2(CO) (4), and then all-trans-RuCl2(PO)2(CO)2 (3), via dissociation of the Ru-O bonds. Reaction of 1 with CO at elevated temperatures gives a new cis-dicarbonyl isomer. RuCl2(PO)2(CO)2 (5), which has trans phosphines. Unlike 4, complex 5 does not readily lose CO thermally; however, it is photochemically converted to a mixture of 3 and 4. Closely related reactions are observed when 1 is treated with tert-butyl isocyanide and the species RuCl2(PO)2(t-BuNC)2 (6) and RuCl2(PO)2(t-BuNC) (7) were identified spectroscopically (and isolated for 6). A reaction scheme rationalizing the formation of 3, 4, 5, 6, and 7 is presented and the results are discussed in light of the known work on phosphinoanisole-transition-metal complexes.

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