Synthesis, characterization, and oxygen atom transfer reactions of {HB(Me2C3N2H)3}MoO{S 2P(OR)2} and {HB(Me2C3N2H)3}MoO 21-S2P(OEt)2}

Sue A Roberts, Charles G. Young, W. E. Cleland, Richard B. Ortega, John H. Enemark

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Abstract

The compounds {HB(Me2pz)3}MoO{S2P(OEt)2} (1a) and {HB(Me2pz)3}MoO2{S2P(OEt) 2} (2) containing bidentate and monodentate S2P(OEt)2- ligands, respectively, have been prepared by the reaction of Mo2O3{S2P(OEt)2}4 with K{HB(Me2pz)3} {HB(Me2pz)3}MoO{S2P(OEt)2} and its analogue {HB(Me2pz)3}MoO{S2P(OMe)2} have also been prepared in higher yield by the reaction of Mo2O3{S2P(OEt)2}4 with Ph3P followed by reaction with K{HB(Me2pz)3}. Both 1a and 2 have been structurally characterized by X-ray crystallography. The blue Mo(IV) compound 1a crystallizes in the monoclinic space group P21/c with a = 17.987 (3) Å, b = 8.219 (3) Å, c = 18.681 (7) Å, β = 104.88 (2)°, and Z = 4. The molybdenum atom is six-coordinate and facially coordinated by the tridentate HB(Me2pz)3- ligand, by one terminal oxo ligand (Mo=O = 1.644 (6) Å) and by the bidentate S2P(OEt)2- ligand. The gold-colored Mo(VI) complex 2 crystallizes as the toluene hemisolvate in the triclinic space group P1 with a = 8.421 (1) Å, b = 12.654 (6) Å, c = 15.240 (5) Å, α = 87.77 (3)°, β = 81.36 (2)°, γ = 74.37 (3)°, and Z = 2. The molybdenum atom is six-coordinate with a tridentate HB(Me2Pz)3- ligand, two terminal oxo ligands (Mo=O = 1.690 (2) and 1.697 (2) Å), and a monodentate S2P(OEt)2- ligand. The S2P(OEt)2- ligand adopts an extended geometry, and the uncoordinated sulfur atom is 5.42 Å from the molybdenum atom. Compound 1a reduces Me2SO to Me2S. The kinetic data can be fit to a second-order rate law with k = 5.46 (6) × 10-5 (M s)-1 in toluene at 40°C. Activation parameters determined from plots of ln (k/T) vs 1/T are ΔH‡ = 15.3 (2) kcal mol-1 and ΔS‡ = -29 (2) cal (mol K)-1. The large negative entropy of activation indicates that an associative mechanism is operative. Compound 2 oxidizes Ph3P to Ph3PO. Again, a second-order rate law is followed: k = 3.4 (1) × 10-3 (M s)-1 in toluene at 25°C. Both complexes catalyze the oxidation of Ph3P by Me2SO.

Original languageEnglish (US)
Pages (from-to)3044-3051
Number of pages8
JournalInorganic Chemistry
Volume27
Issue number17
StatePublished - 1988

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oxygen atoms
Oxygen
Ligands
Atoms
ligands
synthesis
Molybdenum
atoms
Toluene
molybdenum
toluene
Chemical activation
activation
2-hydroxylamino-5-ethyl-5-propylbarbituric acid
X ray crystallography
Sulfur
Gold
crystallography
Entropy
sulfur

ASJC Scopus subject areas

  • Inorganic Chemistry

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Synthesis, characterization, and oxygen atom transfer reactions of {HB(Me2C3N2H)3}MoO{S 2P(OR)2} and {HB(Me2C3N2H)3}MoO 21-S2P(OEt)2}. / Roberts, Sue A; Young, Charles G.; Cleland, W. E.; Ortega, Richard B.; Enemark, John H.

In: Inorganic Chemistry, Vol. 27, No. 17, 1988, p. 3044-3051.

Research output: Contribution to journalArticle

Roberts, Sue A ; Young, Charles G. ; Cleland, W. E. ; Ortega, Richard B. ; Enemark, John H. / Synthesis, characterization, and oxygen atom transfer reactions of {HB(Me2C3N2H)3}MoO{S 2P(OR)2} and {HB(Me2C3N2H)3}MoO 21-S2P(OEt)2}. In: Inorganic Chemistry. 1988 ; Vol. 27, No. 17. pp. 3044-3051.
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title = "Synthesis, characterization, and oxygen atom transfer reactions of {HB(Me2C3N2H)3}MoO{S 2P(OR)2} and {HB(Me2C3N2H)3}MoO 2{η1-S2P(OEt)2}",
abstract = "The compounds {HB(Me2pz)3}MoO{S2P(OEt)2} (1a) and {HB(Me2pz)3}MoO2{S2P(OEt) 2} (2) containing bidentate and monodentate S2P(OEt)2- ligands, respectively, have been prepared by the reaction of Mo2O3{S2P(OEt)2}4 with K{HB(Me2pz)3} {HB(Me2pz)3}MoO{S2P(OEt)2} and its analogue {HB(Me2pz)3}MoO{S2P(OMe)2} have also been prepared in higher yield by the reaction of Mo2O3{S2P(OEt)2}4 with Ph3P followed by reaction with K{HB(Me2pz)3}. Both 1a and 2 have been structurally characterized by X-ray crystallography. The blue Mo(IV) compound 1a crystallizes in the monoclinic space group P21/c with a = 17.987 (3) {\AA}, b = 8.219 (3) {\AA}, c = 18.681 (7) {\AA}, β = 104.88 (2)°, and Z = 4. The molybdenum atom is six-coordinate and facially coordinated by the tridentate HB(Me2pz)3- ligand, by one terminal oxo ligand (Mo=O = 1.644 (6) {\AA}) and by the bidentate S2P(OEt)2- ligand. The gold-colored Mo(VI) complex 2 crystallizes as the toluene hemisolvate in the triclinic space group P1 with a = 8.421 (1) {\AA}, b = 12.654 (6) {\AA}, c = 15.240 (5) {\AA}, α = 87.77 (3)°, β = 81.36 (2)°, γ = 74.37 (3)°, and Z = 2. The molybdenum atom is six-coordinate with a tridentate HB(Me2Pz)3- ligand, two terminal oxo ligands (Mo=O = 1.690 (2) and 1.697 (2) {\AA}), and a monodentate S2P(OEt)2- ligand. The S2P(OEt)2- ligand adopts an extended geometry, and the uncoordinated sulfur atom is 5.42 {\AA} from the molybdenum atom. Compound 1a reduces Me2SO to Me2S. The kinetic data can be fit to a second-order rate law with k = 5.46 (6) × 10-5 (M s)-1 in toluene at 40°C. Activation parameters determined from plots of ln (k/T) vs 1/T are ΔH‡ = 15.3 (2) kcal mol-1 and ΔS‡ = -29 (2) cal (mol K)-1. The large negative entropy of activation indicates that an associative mechanism is operative. Compound 2 oxidizes Ph3P to Ph3PO. Again, a second-order rate law is followed: k = 3.4 (1) × 10-3 (M s)-1 in toluene at 25°C. Both complexes catalyze the oxidation of Ph3P by Me2SO.",
author = "Roberts, {Sue A} and Young, {Charles G.} and Cleland, {W. E.} and Ortega, {Richard B.} and Enemark, {John H.}",
year = "1988",
language = "English (US)",
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pages = "3044--3051",
journal = "Inorganic Chemistry",
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TY - JOUR

T1 - Synthesis, characterization, and oxygen atom transfer reactions of {HB(Me2C3N2H)3}MoO{S 2P(OR)2} and {HB(Me2C3N2H)3}MoO 2{η1-S2P(OEt)2}

AU - Roberts, Sue A

AU - Young, Charles G.

AU - Cleland, W. E.

AU - Ortega, Richard B.

AU - Enemark, John H.

PY - 1988

Y1 - 1988

N2 - The compounds {HB(Me2pz)3}MoO{S2P(OEt)2} (1a) and {HB(Me2pz)3}MoO2{S2P(OEt) 2} (2) containing bidentate and monodentate S2P(OEt)2- ligands, respectively, have been prepared by the reaction of Mo2O3{S2P(OEt)2}4 with K{HB(Me2pz)3} {HB(Me2pz)3}MoO{S2P(OEt)2} and its analogue {HB(Me2pz)3}MoO{S2P(OMe)2} have also been prepared in higher yield by the reaction of Mo2O3{S2P(OEt)2}4 with Ph3P followed by reaction with K{HB(Me2pz)3}. Both 1a and 2 have been structurally characterized by X-ray crystallography. The blue Mo(IV) compound 1a crystallizes in the monoclinic space group P21/c with a = 17.987 (3) Å, b = 8.219 (3) Å, c = 18.681 (7) Å, β = 104.88 (2)°, and Z = 4. The molybdenum atom is six-coordinate and facially coordinated by the tridentate HB(Me2pz)3- ligand, by one terminal oxo ligand (Mo=O = 1.644 (6) Å) and by the bidentate S2P(OEt)2- ligand. The gold-colored Mo(VI) complex 2 crystallizes as the toluene hemisolvate in the triclinic space group P1 with a = 8.421 (1) Å, b = 12.654 (6) Å, c = 15.240 (5) Å, α = 87.77 (3)°, β = 81.36 (2)°, γ = 74.37 (3)°, and Z = 2. The molybdenum atom is six-coordinate with a tridentate HB(Me2Pz)3- ligand, two terminal oxo ligands (Mo=O = 1.690 (2) and 1.697 (2) Å), and a monodentate S2P(OEt)2- ligand. The S2P(OEt)2- ligand adopts an extended geometry, and the uncoordinated sulfur atom is 5.42 Å from the molybdenum atom. Compound 1a reduces Me2SO to Me2S. The kinetic data can be fit to a second-order rate law with k = 5.46 (6) × 10-5 (M s)-1 in toluene at 40°C. Activation parameters determined from plots of ln (k/T) vs 1/T are ΔH‡ = 15.3 (2) kcal mol-1 and ΔS‡ = -29 (2) cal (mol K)-1. The large negative entropy of activation indicates that an associative mechanism is operative. Compound 2 oxidizes Ph3P to Ph3PO. Again, a second-order rate law is followed: k = 3.4 (1) × 10-3 (M s)-1 in toluene at 25°C. Both complexes catalyze the oxidation of Ph3P by Me2SO.

AB - The compounds {HB(Me2pz)3}MoO{S2P(OEt)2} (1a) and {HB(Me2pz)3}MoO2{S2P(OEt) 2} (2) containing bidentate and monodentate S2P(OEt)2- ligands, respectively, have been prepared by the reaction of Mo2O3{S2P(OEt)2}4 with K{HB(Me2pz)3} {HB(Me2pz)3}MoO{S2P(OEt)2} and its analogue {HB(Me2pz)3}MoO{S2P(OMe)2} have also been prepared in higher yield by the reaction of Mo2O3{S2P(OEt)2}4 with Ph3P followed by reaction with K{HB(Me2pz)3}. Both 1a and 2 have been structurally characterized by X-ray crystallography. The blue Mo(IV) compound 1a crystallizes in the monoclinic space group P21/c with a = 17.987 (3) Å, b = 8.219 (3) Å, c = 18.681 (7) Å, β = 104.88 (2)°, and Z = 4. The molybdenum atom is six-coordinate and facially coordinated by the tridentate HB(Me2pz)3- ligand, by one terminal oxo ligand (Mo=O = 1.644 (6) Å) and by the bidentate S2P(OEt)2- ligand. The gold-colored Mo(VI) complex 2 crystallizes as the toluene hemisolvate in the triclinic space group P1 with a = 8.421 (1) Å, b = 12.654 (6) Å, c = 15.240 (5) Å, α = 87.77 (3)°, β = 81.36 (2)°, γ = 74.37 (3)°, and Z = 2. The molybdenum atom is six-coordinate with a tridentate HB(Me2Pz)3- ligand, two terminal oxo ligands (Mo=O = 1.690 (2) and 1.697 (2) Å), and a monodentate S2P(OEt)2- ligand. The S2P(OEt)2- ligand adopts an extended geometry, and the uncoordinated sulfur atom is 5.42 Å from the molybdenum atom. Compound 1a reduces Me2SO to Me2S. The kinetic data can be fit to a second-order rate law with k = 5.46 (6) × 10-5 (M s)-1 in toluene at 40°C. Activation parameters determined from plots of ln (k/T) vs 1/T are ΔH‡ = 15.3 (2) kcal mol-1 and ΔS‡ = -29 (2) cal (mol K)-1. The large negative entropy of activation indicates that an associative mechanism is operative. Compound 2 oxidizes Ph3P to Ph3PO. Again, a second-order rate law is followed: k = 3.4 (1) × 10-3 (M s)-1 in toluene at 25°C. Both complexes catalyze the oxidation of Ph3P by Me2SO.

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JO - Inorganic Chemistry

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