Reactions of the dinuclear ruthenium complex {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4, featuring a doubly linked dicyclopentadienyl ligand

Maxim V. Ovchinnikov, David P. Klein, Ilia A. Guzei, Moon Gun Choi, Robert J. Angelici

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

The complex {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4 (1), which features the doubly linked dicyclopentadienyl ligand (η5-C5H3)2(SiMe2) 2, reacts with phosphines (PMe3, PCy3, PPh3) to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)(μ-CO)2(PR3) (2a-c), with halogens X2 (X = Cl, Br, I) to give the Ru-Ru-cleaved products {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(X)2 (3a-c), with X2 and AgTfO to give [{(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(μ-X)]+TfO- (X = Cl, Br, I; 4a-c), and with SnCl2 to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(μ-SnCl2) (5), resulting from the insertion of SnCl2 into the Ru-Ru bond. Reduction of 1 with Na/Hg generates [{(η5-C5H3)2(SiMe2) 2}Ru2(CO)4]2- (6), which reacts with (η5-C5H5)2TiCl2 to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4{μ-Ti(η5-C5 H5)2} (7). Ultraviolet photolysis of 1 with diphenylacetylene and phenylacetylene yields a series of five dinuclear Ru complexes (8-10, 12, 13) containing one or two bridging acetylene units. The rigidity of the doubly linked (η5-C5H3)2(SiMe2) 2 ligand substantially influences the reactivity and structures of the complexes. Molecular structures of 1, 2a, 3c, 5, 9, 10, and 12 as determined by X-ray diffraction studies are also presented.

Original languageEnglish
Pages (from-to)617-627
Number of pages11
JournalOrganometallics
Volume21
Issue number4
DOIs
Publication statusPublished - 2002 Feb 18

Fingerprint

Ruthenium
Carbon Monoxide
ruthenium
Ligands
ligands
rigidity
phosphines
acetylene
halogens
photolysis
insertion
molecular structure
reactivity
products
diffraction
Phosphines
x rays
Acetylene
Halogens
Photolysis

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Ovchinnikov, Maxim V. ; Klein, David P. ; Guzei, Ilia A. ; Choi, Moon Gun ; Angelici, Robert J. / Reactions of the dinuclear ruthenium complex {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4, featuring a doubly linked dicyclopentadienyl ligand. In: Organometallics. 2002 ; Vol. 21, No. 4. pp. 617-627.
@article{90d892e215154037b8e3cb6a05a8b4ac,
title = "Reactions of the dinuclear ruthenium complex {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4, featuring a doubly linked dicyclopentadienyl ligand",
abstract = "The complex {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4 (1), which features the doubly linked dicyclopentadienyl ligand (η5-C5H3)2(SiMe2) 2, reacts with phosphines (PMe3, PCy3, PPh3) to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)(μ-CO)2(PR3) (2a-c), with halogens X2 (X = Cl, Br, I) to give the Ru-Ru-cleaved products {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(X)2 (3a-c), with X2 and AgTfO to give [{(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(μ-X)]+TfO- (X = Cl, Br, I; 4a-c), and with SnCl2 to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(μ-SnCl2) (5), resulting from the insertion of SnCl2 into the Ru-Ru bond. Reduction of 1 with Na/Hg generates [{(η5-C5H3)2(SiMe2) 2}Ru2(CO)4]2- (6), which reacts with (η5-C5H5)2TiCl2 to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4{μ-Ti(η5-C5 H5)2} (7). Ultraviolet photolysis of 1 with diphenylacetylene and phenylacetylene yields a series of five dinuclear Ru complexes (8-10, 12, 13) containing one or two bridging acetylene units. The rigidity of the doubly linked (η5-C5H3)2(SiMe2) 2 ligand substantially influences the reactivity and structures of the complexes. Molecular structures of 1, 2a, 3c, 5, 9, 10, and 12 as determined by X-ray diffraction studies are also presented.",
author = "Ovchinnikov, {Maxim V.} and Klein, {David P.} and Guzei, {Ilia A.} and Choi, {Moon Gun} and Angelici, {Robert J.}",
year = "2002",
month = "2",
day = "18",
doi = "10.1021/om010674y",
language = "English",
volume = "21",
pages = "617--627",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "4",

}

Reactions of the dinuclear ruthenium complex {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4, featuring a doubly linked dicyclopentadienyl ligand. / Ovchinnikov, Maxim V.; Klein, David P.; Guzei, Ilia A.; Choi, Moon Gun; Angelici, Robert J.

In: Organometallics, Vol. 21, No. 4, 18.02.2002, p. 617-627.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Reactions of the dinuclear ruthenium complex {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4, featuring a doubly linked dicyclopentadienyl ligand

AU - Ovchinnikov, Maxim V.

AU - Klein, David P.

AU - Guzei, Ilia A.

AU - Choi, Moon Gun

AU - Angelici, Robert J.

PY - 2002/2/18

Y1 - 2002/2/18

N2 - The complex {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4 (1), which features the doubly linked dicyclopentadienyl ligand (η5-C5H3)2(SiMe2) 2, reacts with phosphines (PMe3, PCy3, PPh3) to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)(μ-CO)2(PR3) (2a-c), with halogens X2 (X = Cl, Br, I) to give the Ru-Ru-cleaved products {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(X)2 (3a-c), with X2 and AgTfO to give [{(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(μ-X)]+TfO- (X = Cl, Br, I; 4a-c), and with SnCl2 to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(μ-SnCl2) (5), resulting from the insertion of SnCl2 into the Ru-Ru bond. Reduction of 1 with Na/Hg generates [{(η5-C5H3)2(SiMe2) 2}Ru2(CO)4]2- (6), which reacts with (η5-C5H5)2TiCl2 to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4{μ-Ti(η5-C5 H5)2} (7). Ultraviolet photolysis of 1 with diphenylacetylene and phenylacetylene yields a series of five dinuclear Ru complexes (8-10, 12, 13) containing one or two bridging acetylene units. The rigidity of the doubly linked (η5-C5H3)2(SiMe2) 2 ligand substantially influences the reactivity and structures of the complexes. Molecular structures of 1, 2a, 3c, 5, 9, 10, and 12 as determined by X-ray diffraction studies are also presented.

AB - The complex {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4 (1), which features the doubly linked dicyclopentadienyl ligand (η5-C5H3)2(SiMe2) 2, reacts with phosphines (PMe3, PCy3, PPh3) to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)(μ-CO)2(PR3) (2a-c), with halogens X2 (X = Cl, Br, I) to give the Ru-Ru-cleaved products {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(X)2 (3a-c), with X2 and AgTfO to give [{(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(μ-X)]+TfO- (X = Cl, Br, I; 4a-c), and with SnCl2 to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(μ-SnCl2) (5), resulting from the insertion of SnCl2 into the Ru-Ru bond. Reduction of 1 with Na/Hg generates [{(η5-C5H3)2(SiMe2) 2}Ru2(CO)4]2- (6), which reacts with (η5-C5H5)2TiCl2 to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4{μ-Ti(η5-C5 H5)2} (7). Ultraviolet photolysis of 1 with diphenylacetylene and phenylacetylene yields a series of five dinuclear Ru complexes (8-10, 12, 13) containing one or two bridging acetylene units. The rigidity of the doubly linked (η5-C5H3)2(SiMe2) 2 ligand substantially influences the reactivity and structures of the complexes. Molecular structures of 1, 2a, 3c, 5, 9, 10, and 12 as determined by X-ray diffraction studies are also presented.

UR - http://www.scopus.com/inward/record.url?scp=0038157269&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0038157269&partnerID=8YFLogxK

U2 - 10.1021/om010674y

DO - 10.1021/om010674y

M3 - Article

AN - SCOPUS:0038157269

VL - 21

SP - 617

EP - 627

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 4

ER -