Formation of Carbon–Hydrogen and Oxygen–Hydrogen Bonds at Iridium Centers: Addition of H2 and HCl to trans-RIr(CO)L2 (R = Me, OMe; L = PPh3, P(p-tolyl)3)

Jeffrey S. Thompson; Karen A. Bernard; Brian J. Rappoli; Jim D. Atwood

doi:10.1021/om00160a021

Formation of Carbon–Hydrogen and Oxygen–Hydrogen Bonds at Iridium Centers: Addition of H₂ and HCl to trans-RIr(CO)L₂ (R = Me, OMe; L = PPh₃, P(p-tolyl)₃)

Jeffrey S. Thompson
, Karen A. Bernard
, Brian J. Rappoli
, Jim D. Atwood

Chemistry

SUNY Buffalo

Research output: Contribution to journal › Article › peer-review

37 Scopus citations

Abstract

Reaction of trans-RIr(CO)L₂ with HX (R = Me, L = P(p-tolyl)₃, X = H, Cl; R = OMe, L = PPh₃, X = H; R = OMe, L = P(p-tolyl)₃, X = Cl results in RH and HIr(X)₂(CO)L₂. Low-temperature NMR spectra (¹H and³¹P) show that these reactions occur through oxidative-addition, reductive-elimination sequences. A normal deuterium isotope effect is observed (K_H/K_D = 1.4). Formation of the carbon (sp³)–hydrogen bond occurs more readily than formation of the carbon (sp²)–hydrogen bond or the oxygen–hydrogen bond. The nature of the hydrogen source (HX; X = H, Cl) does not significantly affect CH₄ formation but is significant for CH₃OH formation. Considering the geometric and product differences, however, the three types of bonds are formed with remarkably similar barriers.

Original language	English
Pages (from-to)	2727-2731
Number of pages	5
Journal	Organometallics
Volume	9
Issue number	10
DOIs	https://doi.org/10.1021/om00160a021
State	Published - 1990

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title = "Formation of Carbon–Hydrogen and Oxygen–Hydrogen Bonds at Iridium Centers: Addition of H2 and HCl to trans-RIr(CO)L2 (R = Me, OMe; L = PPh3, P(p-tolyl)3)",

abstract = "Reaction of trans-RIr(CO)L2 with HX (R = Me, L = P(p-tolyl)3, X = H, Cl; R = OMe, L = PPh3, X = H; R = OMe, L = P(p-tolyl)3, X = Cl results in RH and HIr(X)2(CO)L2. Low-temperature NMR spectra (1H and31P) show that these reactions occur through oxidative-addition, reductive-elimination sequences. A normal deuterium isotope effect is observed (KH/KD = 1.4). Formation of the carbon (sp3)–hydrogen bond occurs more readily than formation of the carbon (sp2)–hydrogen bond or the oxygen–hydrogen bond. The nature of the hydrogen source (HX; X = H, Cl) does not significantly affect CH4 formation but is significant for CH3OH formation. Considering the geometric and product differences, however, the three types of bonds are formed with remarkably similar barriers.",

author = "Thompson, \{Jeffrey S.\} and Bernard, \{Karen A.\} and Rappoli, \{Brian J.\} and Atwood, \{Jim D.\}",

year = "1990",

doi = "10.1021/om00160a021",

language = "English",

volume = "9",

pages = "2727--2731",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Formation of Carbon–Hydrogen and Oxygen–Hydrogen Bonds at Iridium Centers

T2 - Addition of H2 and HCl to trans-RIr(CO)L2 (R = Me, OMe; L = PPh3, P(p-tolyl)3)

AU - Thompson, Jeffrey S.

AU - Bernard, Karen A.

AU - Rappoli, Brian J.

AU - Atwood, Jim D.

PY - 1990

Y1 - 1990

N2 - Reaction of trans-RIr(CO)L2 with HX (R = Me, L = P(p-tolyl)3, X = H, Cl; R = OMe, L = PPh3, X = H; R = OMe, L = P(p-tolyl)3, X = Cl results in RH and HIr(X)2(CO)L2. Low-temperature NMR spectra (1H and31P) show that these reactions occur through oxidative-addition, reductive-elimination sequences. A normal deuterium isotope effect is observed (KH/KD = 1.4). Formation of the carbon (sp3)–hydrogen bond occurs more readily than formation of the carbon (sp2)–hydrogen bond or the oxygen–hydrogen bond. The nature of the hydrogen source (HX; X = H, Cl) does not significantly affect CH4 formation but is significant for CH3OH formation. Considering the geometric and product differences, however, the three types of bonds are formed with remarkably similar barriers.

AB - Reaction of trans-RIr(CO)L2 with HX (R = Me, L = P(p-tolyl)3, X = H, Cl; R = OMe, L = PPh3, X = H; R = OMe, L = P(p-tolyl)3, X = Cl results in RH and HIr(X)2(CO)L2. Low-temperature NMR spectra (1H and31P) show that these reactions occur through oxidative-addition, reductive-elimination sequences. A normal deuterium isotope effect is observed (KH/KD = 1.4). Formation of the carbon (sp3)–hydrogen bond occurs more readily than formation of the carbon (sp2)–hydrogen bond or the oxygen–hydrogen bond. The nature of the hydrogen source (HX; X = H, Cl) does not significantly affect CH4 formation but is significant for CH3OH formation. Considering the geometric and product differences, however, the three types of bonds are formed with remarkably similar barriers.

UR - https://www.scopus.com/pages/publications/0001753237

U2 - 10.1021/om00160a021

DO - 10.1021/om00160a021

M3 - Article

AN - SCOPUS:0001753237

SN - 0276-7333

VL - 9

SP - 2727

EP - 2731

JO - Organometallics

JF - Organometallics

IS - 10

ER -

Formation of Carbon–Hydrogen and Oxygen–Hydrogen Bonds at Iridium Centers: Addition of H₂ and HCl to trans-RIr(CO)L₂ (R = Me, OMe; L = PPh₃, P(p-tolyl)₃)

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