Oxidative addition of group 14 hydrides to an unsaturated metal cluster. Kinetics of addition of HER3 (ER3 = SiEt3, SiPh3, GeBu3, SnBu3, SnPh3) to H2Os3(CO)10

Robert J. Hall; Petr Serguievski; Jerome Keister

doi:10.1021/om000411o

Oxidative addition of group 14 hydrides to an unsaturated metal cluster. Kinetics of addition of HER₃ (ER₃ = SiEt₃, SiPh₃, GeBu₃, SnBu₃, SnPh₃) to H₂Os₃(CO)₁₀

Robert J. Hall
, Petr Serguievski
, Jerome Keister

Chemistry

SUNY Buffalo

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

15 Scopus citations

Abstract

The kinetics and mechanism of oxidative addition of HER₃ = HSiEt₃, HGeBu₃, HSnBu₃, HSnPh₃ to the unsaturated cluster H₂Os₃(CO)₁₀, initially forming H₃Os₃(CO)₁₀(ER₃), are reported. For HSiEt₃ the addition is readily reversible, with an equilibrium constant of 100 M^-1 at 303 K In each case the rate law for the forward reaction is first-order in both reagents. Rate constants (M^-1 s^-1) at 303 K are as follows: HSnBu₃ (23) > HSnPh₃ (1.5) > HGeBu₃ (0.15) > HSiEt₃ (3.8 × 10^-3). Comparisons are made to additions of group 14 element hydrides to 16-electron Ir(I) complexes. The reaction with HSiPh₃, which forms H₃Os₃(CO)₉(SiPh₃) and further addition products, was also examined.

Original language	English
Pages (from-to)	4499-4505
Number of pages	7
Journal	Organometallics
Volume	19
Issue number	22
DOIs	https://doi.org/10.1021/om000411o
State	Published - Oct 30 2000

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title = "Oxidative addition of group 14 hydrides to an unsaturated metal cluster. Kinetics of addition of HER3 (ER3 = SiEt3, SiPh3, GeBu3, SnBu3, SnPh3) to H2Os3(CO)10",

abstract = "The kinetics and mechanism of oxidative addition of HER3 = HSiEt3, HGeBu3, HSnBu3, HSnPh3 to the unsaturated cluster H2Os3(CO)10, initially forming H3Os3(CO)10(ER3), are reported. For HSiEt3 the addition is readily reversible, with an equilibrium constant of 100 M-1 at 303 K In each case the rate law for the forward reaction is first-order in both reagents. Rate constants (M-1 s-1) at 303 K are as follows: HSnBu3 (23) > HSnPh3 (1.5) > HGeBu3 (0.15) > HSiEt3 (3.8 × 10-3). Comparisons are made to additions of group 14 element hydrides to 16-electron Ir(I) complexes. The reaction with HSiPh3, which forms H3Os3(CO)9(SiPh3) and further addition products, was also examined.",

author = "Hall, \{Robert J.\} and Petr Serguievski and Jerome Keister",

year = "2000",

month = oct,

day = "30",

doi = "10.1021/om000411o",

language = "English",

volume = "19",

pages = "4499--4505",

journal = "Organometallics",

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publisher = "American Chemical Society",

number = "22",

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TY - JOUR

T1 - Oxidative addition of group 14 hydrides to an unsaturated metal cluster. Kinetics of addition of HER3 (ER3 = SiEt3, SiPh3, GeBu3, SnBu3, SnPh3) to H2Os3(CO)10

AU - Hall, Robert J.

AU - Serguievski, Petr

AU - Keister, Jerome

PY - 2000/10/30

Y1 - 2000/10/30

N2 - The kinetics and mechanism of oxidative addition of HER3 = HSiEt3, HGeBu3, HSnBu3, HSnPh3 to the unsaturated cluster H2Os3(CO)10, initially forming H3Os3(CO)10(ER3), are reported. For HSiEt3 the addition is readily reversible, with an equilibrium constant of 100 M-1 at 303 K In each case the rate law for the forward reaction is first-order in both reagents. Rate constants (M-1 s-1) at 303 K are as follows: HSnBu3 (23) > HSnPh3 (1.5) > HGeBu3 (0.15) > HSiEt3 (3.8 × 10-3). Comparisons are made to additions of group 14 element hydrides to 16-electron Ir(I) complexes. The reaction with HSiPh3, which forms H3Os3(CO)9(SiPh3) and further addition products, was also examined.

AB - The kinetics and mechanism of oxidative addition of HER3 = HSiEt3, HGeBu3, HSnBu3, HSnPh3 to the unsaturated cluster H2Os3(CO)10, initially forming H3Os3(CO)10(ER3), are reported. For HSiEt3 the addition is readily reversible, with an equilibrium constant of 100 M-1 at 303 K In each case the rate law for the forward reaction is first-order in both reagents. Rate constants (M-1 s-1) at 303 K are as follows: HSnBu3 (23) > HSnPh3 (1.5) > HGeBu3 (0.15) > HSiEt3 (3.8 × 10-3). Comparisons are made to additions of group 14 element hydrides to 16-electron Ir(I) complexes. The reaction with HSiPh3, which forms H3Os3(CO)9(SiPh3) and further addition products, was also examined.

UR - https://www.scopus.com/pages/publications/0034294577

U2 - 10.1021/om000411o

DO - 10.1021/om000411o

M3 - Article

AN - SCOPUS:0034294577

SN - 0276-7333

VL - 19

SP - 4499

EP - 4505

JO - Organometallics

JF - Organometallics

IS - 22

ER -

Oxidative addition of group 14 hydrides to an unsaturated metal cluster. Kinetics of addition of HER₃ (ER₃ = SiEt₃, SiPh₃, GeBu₃, SnBu₃, SnPh₃) to H₂Os₃(CO)₁₀

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