Abstract
This work describes preparation and reaction chemistry of a terminal nickel(ii) anilide complex supported by an unsymmetrically substituted diarylamido diphosphine ligand, [N(o-C 6H 4PPh 2)(o-C 6H 4P iPr 2)] - ([Ph-PNP- iPr] -). Treatment of NiCl 2(DME) with H[Ph-PNP- iPr] in THF at room temperature produced [Ph-PNP- iPr]NiCl as green crystals in 82% yield. Salt metathesis of [Ph-PNP- iPr]NiCl with LiNHPh(THF) in THF at -35 °C generated cleanly [Ph-PNP- iPr]NiNHPh as a greenish blue solid. The anilide complex deprotonates protic (e.g., PhOH and PhSH) and aprotic (e.g., trimethylsilylacetylene, phenylacetylene, and acetonitrile) acids in benzene at room temperature to give quantitatively [Ph-PNP- iPr]NiX (X = OPh, SPh, CCSiMe 3, CCPh, CH 2CN). In addition, [Ph-PNP- iPr]NiNHPh also behaves as a nucleophile to react with acetyl chloride to yield [Ph-PNP- iPr]NiCl and N-phenylacetamide quantitatively. Carbonylation of [Ph-PNP- iPr]NiNHPh with carbon monoxide affords cleanly the carbamoyl derivative [Ph-PNP- iPr]Ni[C(O) NHPh]. The relative bond strengths of Ni-E in [Ph-PNP- iPr]NiEPh (E = NH, O, S, CC) are assessed and discussed.
| Original language | English |
|---|---|
| Pages (from-to) | 9004-9011 |
| Number of pages | 8 |
| Journal | Dalton Transactions |
| Volume | 40 |
| Issue number | 35 |
| DOIs | |
| Publication status | Published - 2011 Sep 21 |
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All Science Journal Classification (ASJC) codes
- Inorganic Chemistry
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A terminal nickel(II) anilide complex featuring an unsymmetrically substituted amido pincer ligand : Synthesis and reactivity. / Liang, Lan Chang; Li, Chun Wei; Lee, Pei Ying; Chang, Chih Hsiang; Man Lee, Hon.
In: Dalton Transactions, Vol. 40, No. 35, 21.09.2011, p. 9004-9011.Research output: Contribution to journal › Article
TY - JOUR
T1 - A terminal nickel(II) anilide complex featuring an unsymmetrically substituted amido pincer ligand
T2 - Synthesis and reactivity
AU - Liang, Lan Chang
AU - Li, Chun Wei
AU - Lee, Pei Ying
AU - Chang, Chih Hsiang
AU - Man Lee, Hon
PY - 2011/9/21
Y1 - 2011/9/21
N2 - This work describes preparation and reaction chemistry of a terminal nickel(ii) anilide complex supported by an unsymmetrically substituted diarylamido diphosphine ligand, [N(o-C 6H 4PPh 2)(o-C 6H 4P iPr 2)] - ([Ph-PNP- iPr] -). Treatment of NiCl 2(DME) with H[Ph-PNP- iPr] in THF at room temperature produced [Ph-PNP- iPr]NiCl as green crystals in 82% yield. Salt metathesis of [Ph-PNP- iPr]NiCl with LiNHPh(THF) in THF at -35 °C generated cleanly [Ph-PNP- iPr]NiNHPh as a greenish blue solid. The anilide complex deprotonates protic (e.g., PhOH and PhSH) and aprotic (e.g., trimethylsilylacetylene, phenylacetylene, and acetonitrile) acids in benzene at room temperature to give quantitatively [Ph-PNP- iPr]NiX (X = OPh, SPh, CCSiMe 3, CCPh, CH 2CN). In addition, [Ph-PNP- iPr]NiNHPh also behaves as a nucleophile to react with acetyl chloride to yield [Ph-PNP- iPr]NiCl and N-phenylacetamide quantitatively. Carbonylation of [Ph-PNP- iPr]NiNHPh with carbon monoxide affords cleanly the carbamoyl derivative [Ph-PNP- iPr]Ni[C(O) NHPh]. The relative bond strengths of Ni-E in [Ph-PNP- iPr]NiEPh (E = NH, O, S, CC) are assessed and discussed.
AB - This work describes preparation and reaction chemistry of a terminal nickel(ii) anilide complex supported by an unsymmetrically substituted diarylamido diphosphine ligand, [N(o-C 6H 4PPh 2)(o-C 6H 4P iPr 2)] - ([Ph-PNP- iPr] -). Treatment of NiCl 2(DME) with H[Ph-PNP- iPr] in THF at room temperature produced [Ph-PNP- iPr]NiCl as green crystals in 82% yield. Salt metathesis of [Ph-PNP- iPr]NiCl with LiNHPh(THF) in THF at -35 °C generated cleanly [Ph-PNP- iPr]NiNHPh as a greenish blue solid. The anilide complex deprotonates protic (e.g., PhOH and PhSH) and aprotic (e.g., trimethylsilylacetylene, phenylacetylene, and acetonitrile) acids in benzene at room temperature to give quantitatively [Ph-PNP- iPr]NiX (X = OPh, SPh, CCSiMe 3, CCPh, CH 2CN). In addition, [Ph-PNP- iPr]NiNHPh also behaves as a nucleophile to react with acetyl chloride to yield [Ph-PNP- iPr]NiCl and N-phenylacetamide quantitatively. Carbonylation of [Ph-PNP- iPr]NiNHPh with carbon monoxide affords cleanly the carbamoyl derivative [Ph-PNP- iPr]Ni[C(O) NHPh]. The relative bond strengths of Ni-E in [Ph-PNP- iPr]NiEPh (E = NH, O, S, CC) are assessed and discussed.
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U2 - 10.1039/c1dt10191a
DO - 10.1039/c1dt10191a
M3 - Article
C2 - 21666917
AN - SCOPUS:80052093035
VL - 40
SP - 9004
EP - 9011
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 35
ER -