σ-Acetylide complexes of ruthenium and osmium containing alkynylsilane ligands

Wai Yeung Wong; Chun Kin Wong; Guo Liang Lu

doi:10.1016/S0022-328X(03)00003-2

σ-Acetylide complexes of ruthenium and osmium containing alkynylsilane ligands

Wai Yeung Wong^*, Chun Kin Wong, Guo Liang Lu

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal article › peer-review

32 Citations (Scopus)

Abstract

The use of the ligands, diethynyldiphenylsilane and 1,3-diethynyltetramethyldisiloxane, in the synthesis of Group 8 metal σ-acetylide mononuclear complexes is demonstrated. New complexes trans-[(dppm)₂ClMC≡CSi(Ph)₂C≡CH] (M=Ru 1; Os 2) and trans-[(dppm)₂ClMC≡CSi(Me)₂-O-Si(Me)₂C≡CH] (M=Ru, 3; Os, 4) featuring different silyl units were prepared from a mixture of cis-[M(dppm)₂Cl₂] and HC≡CSi(Ph)₂C≡CH or HC≡CSi(Me)₂-O-Si(Me)₂C≡CH in the presence of NaPF₆ followed by deprotonation with 1,8-diazabicyclo[5.4.0]undec-7-ene. All the new complexes have been fully characterized by FTIR and NMR spectroscopies and fast atom bombardment mass spectrometry. Single-crystal X-ray structures of 1 and 2 confirm that the two diphosphines adopt a trans geometry at the metal centre and one of the terminal ethynyl groups remains intact. Complexes 1-4 show reversible redox chemistry and their half-wave potentials due to the metal centres are less anodic than those for the starting precursors cis-[M(dppm)₂Cl₂] (M=Ru, Os).

Original language	English
Pages (from-to)	27-34
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	671
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(03)00003-2
Publication status	Published - 1 Apr 2003

User-Defined Keywords

Alkynyl complexes
Osmium
Ruthenium
Silane
Siloxane

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10.1016/S0022-328X(03)00003-2

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@article{30d44138b97f4838be52593d5e234b44,

title = "σ-Acetylide complexes of ruthenium and osmium containing alkynylsilane ligands",

abstract = "The use of the ligands, diethynyldiphenylsilane and 1,3-diethynyltetramethyldisiloxane, in the synthesis of Group 8 metal σ-acetylide mononuclear complexes is demonstrated. New complexes trans-[(dppm)2ClMC≡CSi(Ph)2C≡CH] (M=Ru 1; Os 2) and trans-[(dppm)2ClMC≡CSi(Me)2-O-Si(Me)2C≡CH] (M=Ru, 3; Os, 4) featuring different silyl units were prepared from a mixture of cis-[M(dppm)2Cl2] and HC≡CSi(Ph)2C≡CH or HC≡CSi(Me)2-O-Si(Me)2C≡CH in the presence of NaPF6 followed by deprotonation with 1,8-diazabicyclo[5.4.0]undec-7-ene. All the new complexes have been fully characterized by FTIR and NMR spectroscopies and fast atom bombardment mass spectrometry. Single-crystal X-ray structures of 1 and 2 confirm that the two diphosphines adopt a trans geometry at the metal centre and one of the terminal ethynyl groups remains intact. Complexes 1-4 show reversible redox chemistry and their half-wave potentials due to the metal centres are less anodic than those for the starting precursors cis-[M(dppm)2Cl2] (M=Ru, Os).",

keywords = "Alkynyl complexes, Osmium, Ruthenium, Silane, Siloxane",

author = "Wong, {Wai Yeung} and Wong, {Chun Kin} and Lu, {Guo Liang}",

note = "Funding Information: Financial support from the Hong Kong Research Grants Council (HKBU 2054/02P) is gratefully acknowledged.",

year = "2003",

month = apr,

day = "1",

doi = "10.1016/S0022-328X(03)00003-2",

language = "English",

volume = "671",

pages = "27--34",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1-2",

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TY - JOUR

T1 - σ-Acetylide complexes of ruthenium and osmium containing alkynylsilane ligands

AU - Wong, Wai Yeung

AU - Wong, Chun Kin

AU - Lu, Guo Liang

N1 - Funding Information: Financial support from the Hong Kong Research Grants Council (HKBU 2054/02P) is gratefully acknowledged.

PY - 2003/4/1

Y1 - 2003/4/1

N2 - The use of the ligands, diethynyldiphenylsilane and 1,3-diethynyltetramethyldisiloxane, in the synthesis of Group 8 metal σ-acetylide mononuclear complexes is demonstrated. New complexes trans-[(dppm)2ClMC≡CSi(Ph)2C≡CH] (M=Ru 1; Os 2) and trans-[(dppm)2ClMC≡CSi(Me)2-O-Si(Me)2C≡CH] (M=Ru, 3; Os, 4) featuring different silyl units were prepared from a mixture of cis-[M(dppm)2Cl2] and HC≡CSi(Ph)2C≡CH or HC≡CSi(Me)2-O-Si(Me)2C≡CH in the presence of NaPF6 followed by deprotonation with 1,8-diazabicyclo[5.4.0]undec-7-ene. All the new complexes have been fully characterized by FTIR and NMR spectroscopies and fast atom bombardment mass spectrometry. Single-crystal X-ray structures of 1 and 2 confirm that the two diphosphines adopt a trans geometry at the metal centre and one of the terminal ethynyl groups remains intact. Complexes 1-4 show reversible redox chemistry and their half-wave potentials due to the metal centres are less anodic than those for the starting precursors cis-[M(dppm)2Cl2] (M=Ru, Os).

AB - The use of the ligands, diethynyldiphenylsilane and 1,3-diethynyltetramethyldisiloxane, in the synthesis of Group 8 metal σ-acetylide mononuclear complexes is demonstrated. New complexes trans-[(dppm)2ClMC≡CSi(Ph)2C≡CH] (M=Ru 1; Os 2) and trans-[(dppm)2ClMC≡CSi(Me)2-O-Si(Me)2C≡CH] (M=Ru, 3; Os, 4) featuring different silyl units were prepared from a mixture of cis-[M(dppm)2Cl2] and HC≡CSi(Ph)2C≡CH or HC≡CSi(Me)2-O-Si(Me)2C≡CH in the presence of NaPF6 followed by deprotonation with 1,8-diazabicyclo[5.4.0]undec-7-ene. All the new complexes have been fully characterized by FTIR and NMR spectroscopies and fast atom bombardment mass spectrometry. Single-crystal X-ray structures of 1 and 2 confirm that the two diphosphines adopt a trans geometry at the metal centre and one of the terminal ethynyl groups remains intact. Complexes 1-4 show reversible redox chemistry and their half-wave potentials due to the metal centres are less anodic than those for the starting precursors cis-[M(dppm)2Cl2] (M=Ru, Os).

KW - Alkynyl complexes

KW - Osmium

KW - Ruthenium

KW - Silane

KW - Siloxane

UR - http://www.scopus.com/inward/record.url?scp=0037389038&partnerID=8YFLogxK

U2 - 10.1016/S0022-328X(03)00003-2

DO - 10.1016/S0022-328X(03)00003-2

M3 - Journal article

AN - SCOPUS:0037389038

SN - 0022-328X

VL - 671

SP - 27

EP - 34

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -

σ-Acetylide complexes of ruthenium and osmium containing alkynylsilane ligands

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