Details
| Original language | English |
|---|---|
| Pages (from-to) | 6051-6060 |
| Number of pages | 10 |
| Journal | European Journal of Inorganic Chemistry |
| Volume | 2014 |
| Issue number | 35 |
| Publication status | Published - 6 Nov 2014 |
Abstract
While phosphane-tethered cyclopentadienyl complexes with tertiary phosphane moieties have extensively been investigated for many metals, this is not the case for such complexes with a secondary phosphane tether. Only a few representatives of such complexes with early-transition-metals are known. Here, we report the first late-transition-metal cyclopentadienyl chelate complexes with silylphosphane or secondary phosphane tethers. The respective ligand system is generated by nucleophilic opening of spiro[2.4]hepta-4,6-diene with lithium tert-butylphosphide. The anionic ligand is trapped with iron(II) chloride with formation of the respective ferrocene derivative. Treatment of lithium tert-butylphosphide with tert-butylchlorodimethylsilane or with chlorotriisopropylsilane affords the respective secondary silylphosphanes. Deprotonation, reaction with spiro[2.4]hepta-4,6-diene, followed by treatment with nickel dihalide complexes affords the respective nickel cyclopentadienylalkylsilylphosphane chelates as the first representatives of their kind. Their halide ligands can easily be exchanged by methylation with methyllithium or by reaction with trimethylsilyl cyanide to give the respective cyano chelate. Under the chromatographic conditions applied, this complex undergoes a protiodesilylation to give the first secondary cyclopentadienylalkylphosphane chelate of a late-transition-metal, which has been characterized by X-ray crystallographic analysis. Alternatively, deprotonation of the extremely sterically crowded primary (2,4,6-tri-tert-butylphenyl)phosphane followed by nucleophilic ring opening of spiro[2.4]hepta-4,6-diene and reaction of the anionic ligand system with NiBr2(thf)2 directly affords the respective cyclopentadienylalkylphosphane nickel chelate with a secondary phosphane ligand.
Keywords
- Arene ligands, Chelates, Nickel, Phosphane ligands, Transition metals
ASJC Scopus subject areas
- Chemistry(all)
- Inorganic Chemistry
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In: European Journal of Inorganic Chemistry, Vol. 2014, No. 35, 06.11.2014, p. 6051-6060.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - The first late-transition-metal cyclopentadienyl chelate complexes with silylphosphane or secondary phosphane tethers
AU - Werner, Irina
AU - Butenschön, Holger
PY - 2014/11/6
Y1 - 2014/11/6
N2 - While phosphane-tethered cyclopentadienyl complexes with tertiary phosphane moieties have extensively been investigated for many metals, this is not the case for such complexes with a secondary phosphane tether. Only a few representatives of such complexes with early-transition-metals are known. Here, we report the first late-transition-metal cyclopentadienyl chelate complexes with silylphosphane or secondary phosphane tethers. The respective ligand system is generated by nucleophilic opening of spiro[2.4]hepta-4,6-diene with lithium tert-butylphosphide. The anionic ligand is trapped with iron(II) chloride with formation of the respective ferrocene derivative. Treatment of lithium tert-butylphosphide with tert-butylchlorodimethylsilane or with chlorotriisopropylsilane affords the respective secondary silylphosphanes. Deprotonation, reaction with spiro[2.4]hepta-4,6-diene, followed by treatment with nickel dihalide complexes affords the respective nickel cyclopentadienylalkylsilylphosphane chelates as the first representatives of their kind. Their halide ligands can easily be exchanged by methylation with methyllithium or by reaction with trimethylsilyl cyanide to give the respective cyano chelate. Under the chromatographic conditions applied, this complex undergoes a protiodesilylation to give the first secondary cyclopentadienylalkylphosphane chelate of a late-transition-metal, which has been characterized by X-ray crystallographic analysis. Alternatively, deprotonation of the extremely sterically crowded primary (2,4,6-tri-tert-butylphenyl)phosphane followed by nucleophilic ring opening of spiro[2.4]hepta-4,6-diene and reaction of the anionic ligand system with NiBr2(thf)2 directly affords the respective cyclopentadienylalkylphosphane nickel chelate with a secondary phosphane ligand.
AB - While phosphane-tethered cyclopentadienyl complexes with tertiary phosphane moieties have extensively been investigated for many metals, this is not the case for such complexes with a secondary phosphane tether. Only a few representatives of such complexes with early-transition-metals are known. Here, we report the first late-transition-metal cyclopentadienyl chelate complexes with silylphosphane or secondary phosphane tethers. The respective ligand system is generated by nucleophilic opening of spiro[2.4]hepta-4,6-diene with lithium tert-butylphosphide. The anionic ligand is trapped with iron(II) chloride with formation of the respective ferrocene derivative. Treatment of lithium tert-butylphosphide with tert-butylchlorodimethylsilane or with chlorotriisopropylsilane affords the respective secondary silylphosphanes. Deprotonation, reaction with spiro[2.4]hepta-4,6-diene, followed by treatment with nickel dihalide complexes affords the respective nickel cyclopentadienylalkylsilylphosphane chelates as the first representatives of their kind. Their halide ligands can easily be exchanged by methylation with methyllithium or by reaction with trimethylsilyl cyanide to give the respective cyano chelate. Under the chromatographic conditions applied, this complex undergoes a protiodesilylation to give the first secondary cyclopentadienylalkylphosphane chelate of a late-transition-metal, which has been characterized by X-ray crystallographic analysis. Alternatively, deprotonation of the extremely sterically crowded primary (2,4,6-tri-tert-butylphenyl)phosphane followed by nucleophilic ring opening of spiro[2.4]hepta-4,6-diene and reaction of the anionic ligand system with NiBr2(thf)2 directly affords the respective cyclopentadienylalkylphosphane nickel chelate with a secondary phosphane ligand.
KW - Arene ligands
KW - Chelates
KW - Nickel
KW - Phosphane ligands
KW - Transition metals
UR - http://www.scopus.com/inward/record.url?scp=84916203069&partnerID=8YFLogxK
U2 - 10.1002/ejic.201402886
DO - 10.1002/ejic.201402886
M3 - Article
AN - SCOPUS:84916203069
VL - 2014
SP - 6051
EP - 6060
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
SN - 1434-1948
IS - 35
ER -