Synthesis and properties of (η5-6,6-dimethylcyclohexadienyl)molybdenum ((dmCh)MoLn) complexes. X-ray structure of [(dmCh) (CO)2Mo]2

Peter T. DiMauro, Peter T. Wolczanski, L. Párkányí, Helen Hurrell Petach

Research output: Article

17 Citations (Scopus)

Abstract

The ancillary character of the 6,6-dimethylcyclohexadienyl ligand (dmCh) was examined via the syntheses of various (dmCh)MoLn derivatives. Treatment of (diglyme)Mo(CO)3 with K(dmCh) afforded [K(diglyme)n][dmCh)Mo(CO)3] (1, 85%), which was converted to (dmCh)Mo(CO)3I (2) by I2 in low yield. The addition of HgI2 to 2.0 equiv of 1 produced [(dmCh)Mo(CO)3]2Hg (3, 77%); iodination of 3 generated 2 in 65% yield. Photolysis of 3 provided the dimer, [(dmCh)Mo(CO)3]2 (4), which was most conveniently prepared via [Cp2Fe]PF6 oxidation of 1 (57%). Thermolysis of 4 yielded a triply bonded dimer, [(dmCh)Mo(CO)2]2 (5, 80%), that contains a 2.508-Å Mo≡Mo bond and two semibridging carbonyls. Crystal data for 5: Cu Kα, triclinic, P1, a = 9.654 (1) Å, b = 8.658 (1) Å, c = 12.608 (2) Á, α = 93.44 (1)°, β = 104.80 (1)°, γ = 100.79 (1)°, Z = 2, T = 23°C, R = 0.049, Rw = 0.036, 2518 reflection (|Fo| ≥ 3σ(Fo)). Anion 1 (Ea = +0.14 V) and singly bonded dimer 4 (Ec = -0.60 V) were observed to be electrochemically coupled via either an ECE or an ECC process; 5 displayed a reversible reduction at -1.10 V. Diazald reacted with 1 to form (dmCh)Mo(CO)2NO (6, 46%); exposure of 6 to PPh3 and PMe3 resulted in the synthesis of (dmCh)Mo(PPh3)(NO)CO (7) and (dmCh)Mo(PMe3)(NO)CO (9) in modest yield, the latter via (η1-dmCh)Mo(PMe3)2(CO)2NO (8). The characteristics of these complexes, as compared with cyclopentadienyl congeners, are consistent with an assessment of dmCh as a strong-field ligand.

Original languageEnglish
Pages (from-to)1097-1106
Number of pages10
JournalOrganometallics
Volume9
Issue number4
Publication statusPublished - 1990

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Molybdenum
Carbon Monoxide
molybdenum
X rays
synthesis
x rays
Dimers
diazalo
dimers
Ligands
congeners
Thermolysis
ligands
Photolysis
Anions
photolysis

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Synthesis and properties of (η5-6,6-dimethylcyclohexadienyl)molybdenum ((dmCh)MoLn) complexes. X-ray structure of [(dmCh) (CO)2Mo]2. / DiMauro, Peter T.; Wolczanski, Peter T.; Párkányí, L.; Petach, Helen Hurrell.

In: Organometallics, Vol. 9, No. 4, 1990, p. 1097-1106.

Research output: Article

DiMauro, Peter T. ; Wolczanski, Peter T. ; Párkányí, L. ; Petach, Helen Hurrell. / Synthesis and properties of (η5-6,6-dimethylcyclohexadienyl)molybdenum ((dmCh)MoLn) complexes. X-ray structure of [(dmCh) (CO)2Mo]2. In: Organometallics. 1990 ; Vol. 9, No. 4. pp. 1097-1106.
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title = "Synthesis and properties of (η5-6,6-dimethylcyclohexadienyl)molybdenum ((dmCh)MoLn) complexes. X-ray structure of [(dmCh) (CO)2Mo]2",
abstract = "The ancillary character of the 6,6-dimethylcyclohexadienyl ligand (dmCh) was examined via the syntheses of various (dmCh)MoLn derivatives. Treatment of (diglyme)Mo(CO)3 with K(dmCh) afforded [K(diglyme)n][dmCh)Mo(CO)3] (1, 85{\%}), which was converted to (dmCh)Mo(CO)3I (2) by I2 in low yield. The addition of HgI2 to 2.0 equiv of 1 produced [(dmCh)Mo(CO)3]2Hg (3, 77{\%}); iodination of 3 generated 2 in 65{\%} yield. Photolysis of 3 provided the dimer, [(dmCh)Mo(CO)3]2 (4), which was most conveniently prepared via [Cp2Fe]PF6 oxidation of 1 (57{\%}). Thermolysis of 4 yielded a triply bonded dimer, [(dmCh)Mo(CO)2]2 (5, 80{\%}), that contains a 2.508-{\AA} Mo≡Mo bond and two semibridging carbonyls. Crystal data for 5: Cu Kα, triclinic, P1, a = 9.654 (1) {\AA}, b = 8.658 (1) {\AA}, c = 12.608 (2) {\'A}, α = 93.44 (1)°, β = 104.80 (1)°, γ = 100.79 (1)°, Z = 2, T = 23°C, R = 0.049, Rw = 0.036, 2518 reflection (|Fo| ≥ 3σ(Fo)). Anion 1 (Ea = +0.14 V) and singly bonded dimer 4 (Ec = -0.60 V) were observed to be electrochemically coupled via either an ECE or an ECC process; 5 displayed a reversible reduction at -1.10 V. Diazald reacted with 1 to form (dmCh)Mo(CO)2NO (6, 46{\%}); exposure of 6 to PPh3 and PMe3 resulted in the synthesis of (dmCh)Mo(PPh3)(NO)CO (7) and (dmCh)Mo(PMe3)(NO)CO (9) in modest yield, the latter via (η1-dmCh)Mo(PMe3)2(CO)2NO (8). The characteristics of these complexes, as compared with cyclopentadienyl congeners, are consistent with an assessment of dmCh as a strong-field ligand.",
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T1 - Synthesis and properties of (η5-6,6-dimethylcyclohexadienyl)molybdenum ((dmCh)MoLn) complexes. X-ray structure of [(dmCh) (CO)2Mo]2

AU - DiMauro, Peter T.

AU - Wolczanski, Peter T.

AU - Párkányí, L.

AU - Petach, Helen Hurrell

PY - 1990

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N2 - The ancillary character of the 6,6-dimethylcyclohexadienyl ligand (dmCh) was examined via the syntheses of various (dmCh)MoLn derivatives. Treatment of (diglyme)Mo(CO)3 with K(dmCh) afforded [K(diglyme)n][dmCh)Mo(CO)3] (1, 85%), which was converted to (dmCh)Mo(CO)3I (2) by I2 in low yield. The addition of HgI2 to 2.0 equiv of 1 produced [(dmCh)Mo(CO)3]2Hg (3, 77%); iodination of 3 generated 2 in 65% yield. Photolysis of 3 provided the dimer, [(dmCh)Mo(CO)3]2 (4), which was most conveniently prepared via [Cp2Fe]PF6 oxidation of 1 (57%). Thermolysis of 4 yielded a triply bonded dimer, [(dmCh)Mo(CO)2]2 (5, 80%), that contains a 2.508-Å Mo≡Mo bond and two semibridging carbonyls. Crystal data for 5: Cu Kα, triclinic, P1, a = 9.654 (1) Å, b = 8.658 (1) Å, c = 12.608 (2) Á, α = 93.44 (1)°, β = 104.80 (1)°, γ = 100.79 (1)°, Z = 2, T = 23°C, R = 0.049, Rw = 0.036, 2518 reflection (|Fo| ≥ 3σ(Fo)). Anion 1 (Ea = +0.14 V) and singly bonded dimer 4 (Ec = -0.60 V) were observed to be electrochemically coupled via either an ECE or an ECC process; 5 displayed a reversible reduction at -1.10 V. Diazald reacted with 1 to form (dmCh)Mo(CO)2NO (6, 46%); exposure of 6 to PPh3 and PMe3 resulted in the synthesis of (dmCh)Mo(PPh3)(NO)CO (7) and (dmCh)Mo(PMe3)(NO)CO (9) in modest yield, the latter via (η1-dmCh)Mo(PMe3)2(CO)2NO (8). The characteristics of these complexes, as compared with cyclopentadienyl congeners, are consistent with an assessment of dmCh as a strong-field ligand.

AB - The ancillary character of the 6,6-dimethylcyclohexadienyl ligand (dmCh) was examined via the syntheses of various (dmCh)MoLn derivatives. Treatment of (diglyme)Mo(CO)3 with K(dmCh) afforded [K(diglyme)n][dmCh)Mo(CO)3] (1, 85%), which was converted to (dmCh)Mo(CO)3I (2) by I2 in low yield. The addition of HgI2 to 2.0 equiv of 1 produced [(dmCh)Mo(CO)3]2Hg (3, 77%); iodination of 3 generated 2 in 65% yield. Photolysis of 3 provided the dimer, [(dmCh)Mo(CO)3]2 (4), which was most conveniently prepared via [Cp2Fe]PF6 oxidation of 1 (57%). Thermolysis of 4 yielded a triply bonded dimer, [(dmCh)Mo(CO)2]2 (5, 80%), that contains a 2.508-Å Mo≡Mo bond and two semibridging carbonyls. Crystal data for 5: Cu Kα, triclinic, P1, a = 9.654 (1) Å, b = 8.658 (1) Å, c = 12.608 (2) Á, α = 93.44 (1)°, β = 104.80 (1)°, γ = 100.79 (1)°, Z = 2, T = 23°C, R = 0.049, Rw = 0.036, 2518 reflection (|Fo| ≥ 3σ(Fo)). Anion 1 (Ea = +0.14 V) and singly bonded dimer 4 (Ec = -0.60 V) were observed to be electrochemically coupled via either an ECE or an ECC process; 5 displayed a reversible reduction at -1.10 V. Diazald reacted with 1 to form (dmCh)Mo(CO)2NO (6, 46%); exposure of 6 to PPh3 and PMe3 resulted in the synthesis of (dmCh)Mo(PPh3)(NO)CO (7) and (dmCh)Mo(PMe3)(NO)CO (9) in modest yield, the latter via (η1-dmCh)Mo(PMe3)2(CO)2NO (8). The characteristics of these complexes, as compared with cyclopentadienyl congeners, are consistent with an assessment of dmCh as a strong-field ligand.

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