Synthesis and Structure of K+[iPrN=C=P]-, a 1-Aza-33-phospha-3-alleni
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- 作者：Gerd Becker ; Heike Brombach ; Stephen T. Horner ; Edgar Niecke ; Wolfgang Schwarz ; Rainer Streubel ; and Ernst-Ulrich Wü ; rthwein
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：May 2, 2005
- 年：2005
- 卷：44
- 期：9
- 页码：3080 - 3086
- 全文大小：131K
- 年卷期：v.44,no.9(May 2, 2005)
- ISSN：1520-510X
文摘
2-Isopropyl(trimethylsilyl)amino-1
3-phosphaalkyne 1 reacts with potassium tert-butoxide to form potassium 1-isopropyl-1-aza-33-phospha-3-allenide (2). This compound was structurally characterized as the corresponding 18-crown-6ether complex 3. The molecular structure of 1 was also determined in order to compare the bonding situation inthe anion and the neutral 3-phosphaalkyne. Compound 3 contains a nitrogen-carbon-phosphorus group for whichthe parameters were shown by X-ray structural analysis and quantum chemical calculations to lie between theextrema N-C
P and N=C=P, suggesting reactivity typical of an ambident anion. This is indeed the case, assubsequent reaction of 2 with chlorotrimethylsilane at nitrogen regenerates the 3-phosphaalkyne 1; withchlorotriphenylsilane the new derivative 4 is formed. In contrast, chlorotrimethylstannane reacts at phosphorus,giving the 1-aza-33-phosphaallene isopropyliminomethylidene(trimethylstannyl)phosphane 5.
3-phosphaalkyne 1 reacts with potassium tert-butoxide to form potassium 1-isopropyl-1-aza-33-phospha-3-allenide (2). This compound was structurally characterized as the corresponding 18-crown-6ether complex 3. The molecular structure of 1 was also determined in order to compare the bonding situation inthe anion and the neutral 3-phosphaalkyne. Compound 3 contains a nitrogen-carbon-phosphorus group for whichthe parameters were shown by X-ray structural analysis and quantum chemical calculations to lie between theextrema N-CP and N=C=P, suggesting reactivity typical of an ambident anion. This is indeed the case, assubsequent reaction of 2 with chlorotrimethylsilane at nitrogen regenerates the 3-phosphaalkyne 1; withchlorotriphenylsilane the new derivative 4 is formed. In contrast, chlorotrimethylstannane reacts at phosphorus,giving the 1-aza-33-phosphaallene isopropyliminomethylidene(trimethylstannyl)phosphane 5.