Skip to main content

Lund University Publications

LUND UNIVERSITY LIBRARIES

Reaction of [Os3H2(CO)10] with the diyne Me3SiC2C2SiMe3 and the reactivity of the products towards [Co2(CO)8] : The X-ray structures of [Os3(μ-H)(CO)10 {μ-η1-η2-HC2 (SiMe3)C2(SiMe3)}],[Os3

Clarke, Lionel P. ; Davies, John E. ; Raithby, Paul R. ; Rennie, Moira-Ann ; Shields, Gregory P. and Sparr, Emma LU (2000) In Journal of Organometallic Chemistry 609(1-2). p.169-176
Abstract

The reaction of [Os3H2(CO)10] with Me3SiC2C2SiMe3 affords both [Os3(μ-H) (CO)10{μ-η1-η2-HC 2(SiMe3)C2(SiMe3)}] (1) and [Os3(μ-CO)(CO)9(μ3-η 2-Me3SiC2C2SiMe3)] (2) in good yield, 2 being favoured with an excess of diyne. In 1, one edge of the triosmium unit is bridged by the vinyl moiety of a transformed bis(trimethylsilyl)-1,4-butadiyne ligand that has undergone a hydride transfer and a 1,2-trimethylsilyl shift. Compound 2 is selectively desilylated in methanol to produce a single isomer... (More)

The reaction of [Os3H2(CO)10] with Me3SiC2C2SiMe3 affords both [Os3(μ-H) (CO)10{μ-η1-η2-HC 2(SiMe3)C2(SiMe3)}] (1) and [Os3(μ-CO)(CO)9(μ3-η 2-Me3SiC2C2SiMe3)] (2) in good yield, 2 being favoured with an excess of diyne. In 1, one edge of the triosmium unit is bridged by the vinyl moiety of a transformed bis(trimethylsilyl)-1,4-butadiyne ligand that has undergone a hydride transfer and a 1,2-trimethylsilyl shift. Compound 2 is selectively desilylated in methanol to produce a single isomer of the known cluster [Os3(μ-CO)(CO)9{μ3-η 2-HC2C2SiMe3}] (3). Whereas reaction of 3 with [Co2(CO)8] results in the production of the previously reported cluster [Os3{μ3-η2-:μ-η 2-(Me3SiC2C2H)[Co 2(CO)6]}(μ-CO)(CO)9] (4) and a second product [Os3(μ-H)(CO)9{μ3-η 1:η2-;μ-η2-Me3SiC 2C2[Co2(CO)6]}] (5), the reaction of 1 and 2 results in recovery of the starting material or transfer of the alkyne ligand to the Co2 unit. Compound 4 undergoes a transformation to 5 in visible light. All the cluster complexes have been characterized spectroscopically, and the solid-state structures of 1, 2 and 5 have been determined by single-crystal X-ray diffraction.

(Less)
Please use this url to cite or link to this publication:
author
; ; ; ; and
publishing date
type
Contribution to journal
publication status
published
keywords
Carbonyl cluster, Cobalt, Diyne, Osmium, X-ray crystal structure
in
Journal of Organometallic Chemistry
volume
609
issue
1-2
pages
8 pages
publisher
Elsevier
external identifiers
  • scopus:0000468349
ISSN
0022-328X
DOI
10.1016/S0022-328X(00)00332-6
language
English
LU publication?
no
id
7faf2354-ab69-4471-ad0f-9367061cacfc
date added to LUP
2023-12-07 14:59:18
date last changed
2023-12-11 09:55:28
@article{7faf2354-ab69-4471-ad0f-9367061cacfc,
  abstract     = {{<p>The reaction of [Os<sub>3</sub>H<sub>2</sub>(CO)<sub>10</sub>] with Me<sub>3</sub>SiC<sub>2</sub>C<sub>2</sub>SiMe<sub>3</sub> affords both [Os<sub>3</sub>(μ-H) (CO)<sub>10</sub>{μ-η<sup>1</sup>-η<sup>2</sup>-HC <sub>2</sub>(SiMe<sub>3</sub>)C<sub>2</sub>(SiMe<sub>3</sub>)}] (1) and [Os<sub>3</sub>(μ-CO)(CO)<sub>9</sub>(μ<sub>3</sub>-η <sup>2</sup>-Me<sub>3</sub>SiC<sub>2</sub>C<sub>2</sub>SiMe<sub>3</sub>)] (2) in good yield, 2 being favoured with an excess of diyne. In 1, one edge of the triosmium unit is bridged by the vinyl moiety of a transformed bis(trimethylsilyl)-1,4-butadiyne ligand that has undergone a hydride transfer and a 1,2-trimethylsilyl shift. Compound 2 is selectively desilylated in methanol to produce a single isomer of the known cluster [Os<sub>3</sub>(μ-CO)(CO)<sub>9</sub>{μ<sub>3</sub>-η <sup>2</sup>-HC<sub>2</sub>C<sub>2</sub>SiMe<sub>3</sub>}] (3). Whereas reaction of 3 with [Co<sub>2</sub>(CO)<sub>8</sub>] results in the production of the previously reported cluster [Os<sub>3</sub>{μ<sub>3</sub>-η<sup>2</sup>-:μ-η <sup>2</sup>-(Me<sub>3</sub>SiC<sub>2</sub>C<sub>2</sub>H)[Co <sub>2</sub>(CO)<sub>6</sub>]}(μ-CO)(CO)<sub>9</sub>] (4) and a second product [Os<sub>3</sub>(μ-H)(CO)<sub>9</sub>{μ<sub>3</sub>-η <sup>1</sup>:η<sup>2</sup>-;μ-η<sup>2</sup>-Me<sub>3</sub>SiC <sub>2</sub>C<sub>2</sub>[Co<sub>2</sub>(CO)<sub>6</sub>]}] (5), the reaction of 1 and 2 results in recovery of the starting material or transfer of the alkyne ligand to the Co<sub>2</sub> unit. Compound 4 undergoes a transformation to 5 in visible light. All the cluster complexes have been characterized spectroscopically, and the solid-state structures of 1, 2 and 5 have been determined by single-crystal X-ray diffraction.</p>}},
  author       = {{Clarke, Lionel P. and Davies, John E. and Raithby, Paul R. and Rennie, Moira-Ann and Shields, Gregory P. and Sparr, Emma}},
  issn         = {{0022-328X}},
  keywords     = {{Carbonyl cluster; Cobalt; Diyne; Osmium; X-ray crystal structure}},
  language     = {{eng}},
  month        = {{09}},
  number       = {{1-2}},
  pages        = {{169--176}},
  publisher    = {{Elsevier}},
  series       = {{Journal of Organometallic Chemistry}},
  title        = {{Reaction of [Os<sub>3</sub>H<sub>2</sub>(CO)<sub>10</sub>] with the diyne Me<sub>3</sub>SiC<sub>2</sub>C<sub>2</sub>SiMe<sub>3</sub> and the reactivity of the products towards [Co<sub>2</sub>(CO)<sub>8</sub>] : The X-ray structures of [Os<sub>3</sub>(μ-H)(CO)<sub>10</sub> {μ-η<sup>1</sup>-η<sup>2</sup>-HC<sub>2</sub> (SiMe<sub>3</sub>)C<sub>2</sub>(SiMe<sub>3</sub>)}],[Os<sub>3</sub>}},
  url          = {{http://dx.doi.org/10.1016/S0022-328X(00)00332-6}},
  doi          = {{10.1016/S0022-328X(00)00332-6}},
  volume       = {{609}},
  year         = {{2000}},
}