Kinetic Deuterium Isotope Effects on Ligand Migrations in Metal Hydrides. 21

Julia Bracker-Novak; Sharad Hajela; Michael Lord; Minsheng Zhang; Edward Rosenberg; Roberto Gobetto; Luciano Milone; Domenico Osella

doi:10.1021/om00119a004

Kinetic Deuterium Isotope Effects on Ligand Migrations in Metal Hydrides. 2¹

Julia Bracker-Novak
, Sharad Hajela
, Michael Lord
, Minsheng Zhang
, Edward Rosenberg
, Roberto Gobetto
, Luciano Milone
, Domenico Osella

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

Abstract

Variable-temperature (VT)¹H and¹³C NMR studies of the complexes (µ-X)₂OS₃(CO)₉(µ₃-η²-(CH₃CH₂)₂C₂) (X = H or D) reveal that alkyne migration over the face of the cluster is directly linked to hydride migrations on the metal core as evidenced by a temperature-independent isotope effect (k_HH/k_DD = 1.7). In a related study of the VT¹³C NMR of (µ-x)₂M₃(CO)₉(µ₃-S) (X = H or D; M = Ru, Os) the observation of a k_HH/k_DD = 1.6 for both the osmium and ruthenium complexes demonstrates that the first stage of carbonyl averaging is brought about by hydride migration and not axial‒radial exchange of carbonyl groups, a process that occurs only at higher temperatures. The mechanistic implications of these results are discussed in the context of the reactivity of metal clusters and the dynamic properties of the metal‒hydrogen bond.

Original language	English
Pages (from-to)	1379-1382
Number of pages	4
Journal	Organometallics
Volume	9
Issue number	5
DOIs	https://doi.org/10.1021/om00119a004
Publication status	Published - 1990
Externally published	Yes

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@article{4c8fad5a2fba4e2faddb2be19a743d97,

title = "Kinetic Deuterium Isotope Effects on Ligand Migrations in Metal Hydrides. 21",

abstract = "Variable-temperature (VT)1H and13C NMR studies of the complexes (µ-X)2OS3(CO)9(µ3-η2-(CH3CH2)2C2) (X = H or D) reveal that alkyne migration over the face of the cluster is directly linked to hydride migrations on the metal core as evidenced by a temperature-independent isotope effect (kHH/kDD = 1.7). In a related study of the VT13C NMR of (µ-x)2M3(CO)9(µ3-S) (X = H or D; M = Ru, Os) the observation of a kHH/kDD = 1.6 for both the osmium and ruthenium complexes demonstrates that the first stage of carbonyl averaging is brought about by hydride migration and not axial‒radial exchange of carbonyl groups, a process that occurs only at higher temperatures. The mechanistic implications of these results are discussed in the context of the reactivity of metal clusters and the dynamic properties of the metal‒hydrogen bond.",

author = "Julia Bracker-Novak and Sharad Hajela and Michael Lord and Minsheng Zhang and Edward Rosenberg and Roberto Gobetto and Luciano Milone and Domenico Osella",

year = "1990",

doi = "10.1021/om00119a004",

language = "English",

volume = "9",

pages = "1379--1382",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "5",

}

TY - JOUR

T1 - Kinetic Deuterium Isotope Effects on Ligand Migrations in Metal Hydrides. 21

AU - Bracker-Novak, Julia

AU - Hajela, Sharad

AU - Lord, Michael

AU - Zhang, Minsheng

AU - Rosenberg, Edward

AU - Gobetto, Roberto

AU - Milone, Luciano

AU - Osella, Domenico

PY - 1990

Y1 - 1990

N2 - Variable-temperature (VT)1H and13C NMR studies of the complexes (µ-X)2OS3(CO)9(µ3-η2-(CH3CH2)2C2) (X = H or D) reveal that alkyne migration over the face of the cluster is directly linked to hydride migrations on the metal core as evidenced by a temperature-independent isotope effect (kHH/kDD = 1.7). In a related study of the VT13C NMR of (µ-x)2M3(CO)9(µ3-S) (X = H or D; M = Ru, Os) the observation of a kHH/kDD = 1.6 for both the osmium and ruthenium complexes demonstrates that the first stage of carbonyl averaging is brought about by hydride migration and not axial‒radial exchange of carbonyl groups, a process that occurs only at higher temperatures. The mechanistic implications of these results are discussed in the context of the reactivity of metal clusters and the dynamic properties of the metal‒hydrogen bond.

AB - Variable-temperature (VT)1H and13C NMR studies of the complexes (µ-X)2OS3(CO)9(µ3-η2-(CH3CH2)2C2) (X = H or D) reveal that alkyne migration over the face of the cluster is directly linked to hydride migrations on the metal core as evidenced by a temperature-independent isotope effect (kHH/kDD = 1.7). In a related study of the VT13C NMR of (µ-x)2M3(CO)9(µ3-S) (X = H or D; M = Ru, Os) the observation of a kHH/kDD = 1.6 for both the osmium and ruthenium complexes demonstrates that the first stage of carbonyl averaging is brought about by hydride migration and not axial‒radial exchange of carbonyl groups, a process that occurs only at higher temperatures. The mechanistic implications of these results are discussed in the context of the reactivity of metal clusters and the dynamic properties of the metal‒hydrogen bond.

UR - https://www.scopus.com/pages/publications/0010781799

U2 - 10.1021/om00119a004

DO - 10.1021/om00119a004

M3 - Article

SN - 0276-7333

VL - 9

SP - 1379

EP - 1382

JO - Organometallics

JF - Organometallics

IS - 5

ER -

Kinetic Deuterium Isotope Effects on Ligand Migrations in Metal Hydrides. 2¹

Abstract

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