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A MODEL FOR HOMOGENEOUS HYDRODESULFURIZATION - THE IMPORTANCE OF ETA-2-COORDINATION AND SULFUR COORDINATION IN C-H AND C-S BOND-CLEAVAGE REACTIONS OF THIOPHENE

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A MODEL FOR HOMOGENEOUS HYDRODESULFURIZATION - THE IMPORTANCE OF ETA-2-COORDINATION AND SULFUR COORDINATION IN C-H AND C-S BOND-CLEAVAGE REACTIONS OF THIOPHENE. / DONG, L Z ; DUCKETT, S B ; OHMAN, K F ; JONES, W D .

In: Journal of the American Chemical Society, Vol. 114, No. 1, 01.01.1992, p. 151-160.

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Harvard

DONG, LZ, DUCKETT, SB, OHMAN, KF & JONES, WD 1992, 'A MODEL FOR HOMOGENEOUS HYDRODESULFURIZATION - THE IMPORTANCE OF ETA-2-COORDINATION AND SULFUR COORDINATION IN C-H AND C-S BOND-CLEAVAGE REACTIONS OF THIOPHENE', Journal of the American Chemical Society, vol. 114, no. 1, pp. 151-160.

APA

DONG, L. Z., DUCKETT, S. B., OHMAN, K. F., & JONES, W. D. (1992). A MODEL FOR HOMOGENEOUS HYDRODESULFURIZATION - THE IMPORTANCE OF ETA-2-COORDINATION AND SULFUR COORDINATION IN C-H AND C-S BOND-CLEAVAGE REACTIONS OF THIOPHENE. Journal of the American Chemical Society, 114(1), 151-160.

Vancouver

DONG LZ, DUCKETT SB, OHMAN KF, JONES WD. A MODEL FOR HOMOGENEOUS HYDRODESULFURIZATION - THE IMPORTANCE OF ETA-2-COORDINATION AND SULFUR COORDINATION IN C-H AND C-S BOND-CLEAVAGE REACTIONS OF THIOPHENE. Journal of the American Chemical Society. 1992 Jan 1;114(1):151-160.

Author

DONG, L Z ; DUCKETT, S B ; OHMAN, K F ; JONES, W D . / A MODEL FOR HOMOGENEOUS HYDRODESULFURIZATION - THE IMPORTANCE OF ETA-2-COORDINATION AND SULFUR COORDINATION IN C-H AND C-S BOND-CLEAVAGE REACTIONS OF THIOPHENE. In: Journal of the American Chemical Society. 1992 ; Vol. 114, No. 1. pp. 151-160.

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@article{966fc593157c440aabb8534bf8788d4f,
title = "A MODEL FOR HOMOGENEOUS HYDRODESULFURIZATION - THE IMPORTANCE OF ETA-2-COORDINATION AND SULFUR COORDINATION IN C-H AND C-S BOND-CLEAVAGE REACTIONS OF THIOPHENE",
abstract = "The reaction of (C5Me5)Rh(PMe3)PhH with thiophene at 60-degrees-C produces the C-S cleavage adduct (C5Me5)-Rh(PMe3) (SCH = CHCH = CH) in high yield. Irradiation of (C5Me5)Rh(PMe3)H-2 at -20-degrees-C in the presence of thiophene results in the formation of both the C-S insertion product and the new C-H addition adduct (C5Me5)Rh(PMe3)(2-thienyl)H. The latter can be independently prepared by the reaction of (C5Me5)Rh(PMe3)Cl2 with 2-thienyllithium, followed by LiHBEt3. The 2-thienyl hydride rearranges intramolecularly to the C-S insertion adduct with activation parameters DELTA-H = 25.15 (45) kcal/mol and DELTA-S = 3.0 (2) eu. Preparation with LiDBEt3 generates (C5Me5)Rh(PMe3)(2-thienyl)D, which rearranges to the C-S insertion product in which the deuterium is scrambled over both carbons that were originally adjacent to the sulfur atom. Similarly, the complex (C5Me5)Rh(PMe3)(3-thienyl)H was prepared and observed to isomerize intramolecularly to the 2-thienyl derivative at 23-degrees-C with a rate constant of 1.2 (1) X 10(-3) s-1. The corresponding deuteride complex (C5Me5)Rh(PMe3)(3-thienyl)D was observed to rearrange selectively first to (C5Me5)Rh(PMe3)[2-(3-deuteriothienyl)]H and then to a mixture of the C-S insertion adducts with deuterium attached to either the 3 or 4 carbon. The rearrangements of several methyl derivatives have also been studied and found to occur with similar regiospecificity. Heating of (C5Me5)Rh-(PMe3) PhH in the presence of tetramethylthiophene results in the formation of the S-bound complex, (C5Me5)Rh(PMe3)(SC4Me4). The chloro derivative (C5Me5)Rh(PMe3)(2-thienyl)Cl was found to crystallize in the monoclinic space group P2(1)/c with a = 8.992 (7) angstrom, b = 11.324 (10) angstrom, c = 18.480 (8) angstrom, beta = 91.52 (6)-degrees, V = 1881.0 (2.3), and Z = 4.",
keywords = "TRIOSMIUM CLUSTER COMPLEX, STRAINED-RING THIOETHERS, SINGLE-CRYSTAL SURFACE, CATALYTIC HYDRODESULFURIZATION, MECHANISM, DESULFURIZATION, ACTIVATION, IRON, TRANSFORMATION, HYDROGENOLYSIS",
author = "DONG, {L Z} and DUCKETT, {S B} and OHMAN, {K F} and JONES, {W D}",
year = "1992",
month = "1",
day = "1",
language = "English",
volume = "114",
pages = "151--160",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "1",

}

RIS (suitable for import to EndNote) - Download

TY - JOUR

T1 - A MODEL FOR HOMOGENEOUS HYDRODESULFURIZATION - THE IMPORTANCE OF ETA-2-COORDINATION AND SULFUR COORDINATION IN C-H AND C-S BOND-CLEAVAGE REACTIONS OF THIOPHENE

AU - DONG, L Z

AU - DUCKETT, S B

AU - OHMAN, K F

AU - JONES, W D

PY - 1992/1/1

Y1 - 1992/1/1

N2 - The reaction of (C5Me5)Rh(PMe3)PhH with thiophene at 60-degrees-C produces the C-S cleavage adduct (C5Me5)-Rh(PMe3) (SCH = CHCH = CH) in high yield. Irradiation of (C5Me5)Rh(PMe3)H-2 at -20-degrees-C in the presence of thiophene results in the formation of both the C-S insertion product and the new C-H addition adduct (C5Me5)Rh(PMe3)(2-thienyl)H. The latter can be independently prepared by the reaction of (C5Me5)Rh(PMe3)Cl2 with 2-thienyllithium, followed by LiHBEt3. The 2-thienyl hydride rearranges intramolecularly to the C-S insertion adduct with activation parameters DELTA-H = 25.15 (45) kcal/mol and DELTA-S = 3.0 (2) eu. Preparation with LiDBEt3 generates (C5Me5)Rh(PMe3)(2-thienyl)D, which rearranges to the C-S insertion product in which the deuterium is scrambled over both carbons that were originally adjacent to the sulfur atom. Similarly, the complex (C5Me5)Rh(PMe3)(3-thienyl)H was prepared and observed to isomerize intramolecularly to the 2-thienyl derivative at 23-degrees-C with a rate constant of 1.2 (1) X 10(-3) s-1. The corresponding deuteride complex (C5Me5)Rh(PMe3)(3-thienyl)D was observed to rearrange selectively first to (C5Me5)Rh(PMe3)[2-(3-deuteriothienyl)]H and then to a mixture of the C-S insertion adducts with deuterium attached to either the 3 or 4 carbon. The rearrangements of several methyl derivatives have also been studied and found to occur with similar regiospecificity. Heating of (C5Me5)Rh-(PMe3) PhH in the presence of tetramethylthiophene results in the formation of the S-bound complex, (C5Me5)Rh(PMe3)(SC4Me4). The chloro derivative (C5Me5)Rh(PMe3)(2-thienyl)Cl was found to crystallize in the monoclinic space group P2(1)/c with a = 8.992 (7) angstrom, b = 11.324 (10) angstrom, c = 18.480 (8) angstrom, beta = 91.52 (6)-degrees, V = 1881.0 (2.3), and Z = 4.

AB - The reaction of (C5Me5)Rh(PMe3)PhH with thiophene at 60-degrees-C produces the C-S cleavage adduct (C5Me5)-Rh(PMe3) (SCH = CHCH = CH) in high yield. Irradiation of (C5Me5)Rh(PMe3)H-2 at -20-degrees-C in the presence of thiophene results in the formation of both the C-S insertion product and the new C-H addition adduct (C5Me5)Rh(PMe3)(2-thienyl)H. The latter can be independently prepared by the reaction of (C5Me5)Rh(PMe3)Cl2 with 2-thienyllithium, followed by LiHBEt3. The 2-thienyl hydride rearranges intramolecularly to the C-S insertion adduct with activation parameters DELTA-H = 25.15 (45) kcal/mol and DELTA-S = 3.0 (2) eu. Preparation with LiDBEt3 generates (C5Me5)Rh(PMe3)(2-thienyl)D, which rearranges to the C-S insertion product in which the deuterium is scrambled over both carbons that were originally adjacent to the sulfur atom. Similarly, the complex (C5Me5)Rh(PMe3)(3-thienyl)H was prepared and observed to isomerize intramolecularly to the 2-thienyl derivative at 23-degrees-C with a rate constant of 1.2 (1) X 10(-3) s-1. The corresponding deuteride complex (C5Me5)Rh(PMe3)(3-thienyl)D was observed to rearrange selectively first to (C5Me5)Rh(PMe3)[2-(3-deuteriothienyl)]H and then to a mixture of the C-S insertion adducts with deuterium attached to either the 3 or 4 carbon. The rearrangements of several methyl derivatives have also been studied and found to occur with similar regiospecificity. Heating of (C5Me5)Rh-(PMe3) PhH in the presence of tetramethylthiophene results in the formation of the S-bound complex, (C5Me5)Rh(PMe3)(SC4Me4). The chloro derivative (C5Me5)Rh(PMe3)(2-thienyl)Cl was found to crystallize in the monoclinic space group P2(1)/c with a = 8.992 (7) angstrom, b = 11.324 (10) angstrom, c = 18.480 (8) angstrom, beta = 91.52 (6)-degrees, V = 1881.0 (2.3), and Z = 4.

KW - TRIOSMIUM CLUSTER COMPLEX

KW - STRAINED-RING THIOETHERS

KW - SINGLE-CRYSTAL SURFACE

KW - CATALYTIC HYDRODESULFURIZATION

KW - MECHANISM

KW - DESULFURIZATION

KW - ACTIVATION

KW - IRON

KW - TRANSFORMATION

KW - HYDROGENOLYSIS

M3 - Article

VL - 114

SP - 151

EP - 160

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 1

ER -